WO2002086913A1

WO2002086913A1 - Conductive organic thin film and production method therefor, electrode and electric cable using it

Info

Publication number: WO2002086913A1
Application number: PCT/JP2002/001067
Authority: WO
Inventors: Kazufumi Ogawa; Norihisa Mino; Shinichi Yamamoto
Original assignee: Matsushita Electric Industrial Co., Ltd.
Priority date: 2001-04-17
Filing date: 2002-02-08
Publication date: 2002-10-31
Also published as: EP1381058A1; US20030099845A1; DE60216257D1; CN1463444A; DE60216257T2; TWI298732B; KR100544378B1; EP1381058B1; KR20040030175A; EP1381058A4; CN100585751C

Abstract

A conductive organic thin film comprising terminal bond radicals conjugate-bonded with the surface of a base material (1) or the surface of a base layer (2) formed on the base material, conjugate bond radicals, and organic molecules containing alkyl radicals between the terminal bond radicals and the conjugate bond radicals, wherein the organic molecules are oriented, and the conjugate bond radicals are polymerized with the conjugate bond radicals of other molecules to form a conductive network (34). The network (34) is formed of polypyrrole, polythienylene, polyacetylene, polydiacetylene or polyacene. The polymerization of conjugate bond radicals uses electrolytic oxidation polymerization, catalyst polymerization, and energy beam irradiation polymerization. Accordingly, a conductive organic thin film having conductivity higher than conventional organic conductive films and a production method therefor, and an electrode, cable and electronic device using it are provided.

Description

Description Conductive organic thin film, method for producing the same, electrode and electric cable using the same

The present invention relates to a conductive organic thin film using an organic material and a method for producing the same, an electrode and an electric cable using the same. Further, the present invention relates to a conductive monomolecular film or a monomolecular cumulative film.

Background art

There have been various proposals for organic conductive films. The present applicant has already proposed a conductive film containing a conductive conjugate group such as polyacetylene, polydiacetylene, polyacene (Polyacene;), polyphenylene, polychenylene, polypyrrole, and polyaniline ( JP-A-2 (1990)-27766, USP 5,008,127, EP-A-0385656, EP-A-0339677, EP-A-0552637, USP 5,270,417, JP-A 5 (1993)-87559 Gazette, JP-A-6 (1994) -242352).

In addition, inorganic semiconductor materials such as silicon crystals have been used for electronic devices. Organic electronic devices (hereinafter referred to as organic electronic devices) are disclosed in, for example, Japanese Patent Nos. 2034197 and 2507153. The organic electronic devices described in these publications are organic electronic devices that switch a current flowing between terminals in response to an applied electric field.

The conventional organic conductive film has a problem that the conductivity is lower than that of a metal. In addition, in the case of inorganic crystals that have been used in the past, crystal defects have become a problem as miniaturization has progressed, and there has been a problem that device performance is greatly affected by crystals. There is also the problem of poor flexibility. I got it.

Disclosure of the invention

The present invention has been made in view of the above, and a first object of the present invention is to provide a conductive organic thin film having higher conductivity than a conventional organic conductive film and a method for producing the same.

The second object of the present invention is to provide an electrode made of a conductive organic thin film that is not influenced by crystallinity even if finer processing of 0.1 m or less is performed due to the progress of device densification. An object of the present invention is to provide an organic electronic device having the highest operability.

In order to achieve the above object, the conductive organic thin film of the present invention comprises: a terminal bonding group covalently bonded to a substrate surface or an underlayer surface formed on the substrate; a conjugate bonding group; A conductive organic thin film composed of an organic molecule containing an alkyl group between a conjugate bond group and the organic molecule, wherein the organic molecule is oriented, and the conjugate bond group is linked to a conjugate bond group of another molecule. It is characterized in that it forms a conductive mesh and work by polymerization.

Next, the method for producing a conductive organic thin film of the present invention comprises the following steps: a terminal functional group capable of covalently bonding to the surface of the substrate or the surface of the underlayer formed on the substrate; a functional group capable of conjugate bonding; A chemically adsorbed compound containing an alkyl group between the functional group and the functional group capable of conjugate bonding to the surface of a substrate having active hydrogen on the surface or to which active hydrogen has been added, or the surface of an underlayer formed on the substrate. An organic thin film is formed by being covalently bonded by an elimination reaction to form an organic thin film, and the organic molecules constituting the organic thin film are oriented in a predetermined direction or polymerized while being oriented in a polymerization step. The conjugate-bondable groups are conjugated to each other by at least one polymerization method selected from electrolytic oxidation polymerization, catalyst polymerization, and energy beam irradiation polymerization to form a conductive network. Next, the electrode of the present invention is an electrode formed of a conductive organic thin film transparent at a light wavelength in a visible light region, wherein the conductive organic thin film is formed on a substrate surface or on a substrate. A terminal bonding group covalently bonded to the surface of the underlayer, a conjugated bonding group, and an organic molecule containing an alkyl group between the terminal bonding group and the conjugated bonding group. And the conjugated group is polymerized with a conjugated group of another molecule to form a conductive network.

Next, the electric cable of the present invention is an electric cable including a core wire and a conductive organic thin film formed in a length direction of the surface of the core wire, wherein the conductive organic thin film is formed on a base material surface or A terminal bonding group covalently bonded to the surface of the underlayer formed on the base material; a conjugate bonding group; and an organic molecule including an alkyl group between the terminal bonding group and the conjugate bonding group. Are oriented, and the conjugated group is polymerized with the conjugated group of another molecule to form a conductive network.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1A is a cross-sectional view of a monomolecular film having a conductive network formed in all regions according to Embodiment 1 of the present invention, and FIG. 1B is a cross-sectional view of a monomolecular film having a conductive network formed in a plurality of partial regions. FIG. 1C is a cross-sectional view of a monomolecular film composed of an organic molecule having a conjugated polymerizable functional group therein and having a conductive network formed in a plurality of partial regions.

FIG. 2 is a schematic plan view for explaining the direction of the conductive network according to the first embodiment of the present invention.

FIG. 3A is a plan view of a monolayer in which a conductive network extending in one direction is formed in the entire region in Embodiment 1 of the present invention, and FIG. 3B is a parallel view in which a conductive network extending in one direction is formed in each conductive region. Plan view of a monolayer having various conductive regions, and Fig. 3C shows a conductive network connected in one direction to each conductive region. Plan view of the formed monolayer having conductive regions arranged in a matrix. Fig. 3D shows the direction of the conductive network formed in each conductive region, and the shape of each conductive region is not the same. FIG. 4 is a plan view of a monolayer having conductive regions arranged in a pattern shown in FIG.

FIG. 4A is a cross-sectional view schematically showing a structural example of a monomolecular film formed on a base material according to the first embodiment of the present invention, and FIG. It is sectional drawing of the formed monomolecular film.

FIG. 5A is a schematic perspective view for explaining a rubbing orientation method for tilting (orienting) molecules constituting an organic thin film according to Embodiment 1 of the present invention, FIG. 5B is a perspective view of a photo-alignment method, and FIG. FIG. 4 is a perspective view of a liquid drainage alignment method.

FIG. 6A is a perspective view schematically showing a configuration example in which a conductive region is formed in a selective portion on a base material according to the first embodiment of the present invention, and FIG. 6B is a diagram in which a conductive region is formed in all regions. FIG. 4 is a perspective view in which a plurality of monomolecular films formed are formed on a base material. FIGS. 7A to 7D are cross-sectional views schematically showing examples of a laminated structure of a monomolecular cumulative film formed on a base material according to Embodiment 2 of the present invention. FIG. 7A shows the orientation direction of each monomolecular layer. X-type monomolecular accumulation film with the same direction, Fig. 7B shows Y-type monomolecular accumulation film with the same orientation direction of each monolayer, and Fig. 7C shows different orientation directions for each monolayer. Figure 7D shows an X-type monomolecular cumulative film oriented in one of two orientation directions for each monolayer. FIG. 8A is a cross-sectional view of an electric cable formed on the outer surface of a core wire in Example 12 of the present invention. FIG. 8B is a perspective view of a collective electric wire type electric cable in Embodiment 3 of the present invention. FIG. 9 is a perspective view of a collective electric wire type flat cable according to Embodiment 3 of the present invention.

9A and 9B are cross-sectional views schematically showing an example of the structure of a capacitor using a conductive region formed in a monomolecular film as an electrode according to Embodiment 4 of the present invention. FIG. Each of the two substrates with molecular films Fig. 9B shows a structure in which a monomolecular film having a conductive region is formed on each of two parallel surfaces of the dielectric. FIG. 2 is a cross-sectional view for explaining a step of manufacturing a monomolecular film having a conductive region according to Embodiment 1 and Example 6 of the present invention.FIG. 1OA is formed on a substrate after a monomolecular layer forming step. Monolayer, Figure 10B: Oriented monolayer after tilting process (alignment process), Figure 10C: Conductive region formation by applying voltage to a pair of electrodes formed on the surface in the polymerization electrode formation process The monomolecular film immediately after the start of the process, and FIG. 10D is a monomolecular film having a conductive network formed after the conductive region forming process.

FIGS. 11A to 11F are conceptual diagrams of a manufacturing process of an organic conductive film in Example 2 of the present invention.

FIGS. 12A and 12B are conceptual cross-sectional views illustrating a process for orienting molecules in a molecular layer according to the second embodiment of the present invention.

FIG. 13 is a conceptual cross-sectional view illustrating an organic electronic device according to Example 3 of the present invention.

FIG. 14 is a conceptual cross-sectional view illustrating a liquid crystal display device according to a fourth embodiment of the present invention.

FIG. 15 is a conceptual cross-sectional view illustrating an elector-luminescence (EL) display device according to a fifth embodiment of the present invention.

FIG. 16 is an explanatory diagram showing a method for evaluating the orientation of conductive molecules in Example 14 of the present invention.

FIG. 17 is an NMR chart of the product obtained in Example 1 of the present invention. FIG. 18 is an IR chart of the product obtained in Example 1 of the present invention. 1: substrate (substrate), 2: substrate insulating film, 3: protective coating, 4: monolayer (monolayer), 5: conjugated system (conjugated bond chain), 6: conductive region, 7: metal contact ( 8) Dielectric, 9: Conjugated polymerizable functional group, 11: Insulating substrate, 1 3: Insulating protective film, 14: Monomolecular film composed of organic molecules having a pyrol group, 16: Conductive region having a polypyrrol conductive network, 17: Platinum electrode for electrolytic polymerization, 24: Monomolecular film with oriented organic molecules having pyrrole group, 34: Monomolecular film with polypyrroline-type conductive network, 41: Lapindarol, 42: Rubbing cloth, 43: Polarizing plate, 44, Cleaning Organic solution for

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the reason why the organic thin film has conductivity is that molecules constituting an assembly group of organic molecules are conjugated and polymerized. Here, the conductive network is an aggregate of organic molecules connected by conjugate bonds involved in electric conduction, and is formed of a polymer having a conjugate bond chain (conjugate system). The conductive network is formed in the direction between the electrodes. This conjugated bond chain polymer is not strictly connected in one direction, and it is sufficient that polymer chains in various directions are formed between the electrodes as a whole.

In the present invention, the conductive organic thin film of conductivity (p) is the 1 SZ cm or more, and preferably 1 X 1 0 ² SZ cm or more, more preferably 1 X 1 0 ³ S / cm or more. All above values are for room temperature (25 ° C) without dopant.

The polymerized conjugated group is preferably at least one conjugated group selected from polypyrrole, polychenylene, polyacetylene, polydiacetylene and polyacene. In particular, the conjugated bond is polypyrrole or polychenylene, and the thin film formed by electrolytic oxidation polymerization has high conductivity.

The terminal binding group is preferably at least one bond selected from siloxane (—Sio—) and SiN— bonds.

The terminal linking group includes dehydrochlorination, dealcoholation and It is formed by at least one elimination reaction selected from the cyanate reaction. For example the functional groups of the molecular ends _{- SiCl 3, - Si (0R} ) 3 ( where R is an alkyl group having 1-3 carbon atoms), or - Si (NC0) For _3, on the substrate surface or substrate forming the undercoat layer on the surface - 0H group, -CH0 group, -C00H group, - NH ₂ group,> the active hydrogen that is part of the NH group or the like exists, dehydrochlorination reaction and dealcoholization or removal Isoshianeto reaction As a result, the chemisorbed molecules are covalently bonded to the surface of the substrate or the surface of the underlayer formed on the substrate.

The molecular film formed by this method is referred to in the art as a “chemisorption film” or “self assembling film”, but is referred to as a “chemisorption film” in the present invention. . The formation method is called "chemisorption method".

In the present invention, the orientation of molecules is determined by rubbing orientation treatment, decantation treatment from a reaction solution after covalently bonding molecules to a substrate surface by a desorption reaction, polarized light irradiation treatment, and molecular fluctuation in the polymerization process. Preferably, the conductive region of the organic thin film is transparent to light having a wavelength in the visible region.

The molecular unit forming the conductive network is preferably represented by, for example, the following formula (A) or (B).

(A) X-Si (-0-) _P E 3-p

(B)

(However, in the chemical formulas (A) and (B), X is hydrogen, an organic group containing an ester group or an unsaturated group, Q is an integer of 0 to 10, E is hydrogen or an alkyl group having 13 to 13 carbon atoms) And n is an integer of 2 or more and 25 or less, preferably 10 or more and 20 or less, and p is an integer and is 1, 2 or 3. The compound for forming the conductive network has the following chemical formula: It is a pyrrolyl compound or a thienyl compound represented by (C) or (D).

X-

(However, in the above formulas (C) and (D), X is hydrogen, an organic group containing an ester group or an unsaturated group, q is an integer of 0 to 10, D is a halogen atom, an isocyanate group or An alkoxyl group having 13 to 13 carbon atoms, E is hydrogen or an alkyl group having 1 to 3 carbon atoms, n is an integer of 2 or more and 25 or less, and p is an integer and is 1, 2 or 3.)

The conjugated bondable group, pyrrole group, Choi two alkylene groups, be acetylene group, and at least one good _t the organic molecules be a group selected from diacetylene group is formed on the monomolecular layer preferably . Further, by repeating the monomolecular layer forming step a plurality of times, the monomolecular layers may be stacked to form a monomolecular cumulative film.

In the above formula A or B, when X contains an ester group, a carboxyl group (—COOH) can be introduced by hydrolysis. When X contains an unsaturated group such as a Bier bond, a hydroxyl group (-OH) can be introduced by irradiating an energy beam such as an electron beam or an X-ray in an atmosphere where moisture is present. Further, when X contains an unsaturated group such as a Bier bond, for example, one COH can be introduced by immersion in an aqueous solution of potassium permanganate. In this case, active hydrogen can be introduced, so that the monomolecular film can be further accumulated.

In addition, after the monomolecular layer forming step and the tilting (orienting) step are alternately and repeatedly performed, a conductive network is collectively formed in each monolayer of the monomolecular accumulation film in the conductive network forming step. Thus, a conductive monomolecular accumulation film may be formed.

Further, a conductive monomolecular cumulative film may be formed by repeatedly performing a series of steps including the monomolecular layer forming step, the tilting step, and the conductive network forming step.

As the polymerization method, there is at least one polymerization method selected from electrolytic oxidation polymerization, catalytic polymerization, and energy beam irradiation polymerization. Before forming the conductive network by the electrolytic oxidation, at least one prepolymerization selected from catalytic polymerization and energy linear irradiation polymerization may be performed.

The energy ray is preferably at least one selected from ultraviolet rays, far ultraviolet rays, X-rays and electron beams.

The energy ray is at least one selected from polarized ultraviolet rays, polarized far ultraviolet rays, and polarized X-rays, and the tilt alignment treatment and the formation of the conductive network may be performed simultaneously. When the organic molecule contains a polar functional group, the sensitivity to an applied electric field is high, and the response speed is high. Therefore, the conductivity of the organic thin film can be changed at a high speed. It is considered that the change in the conductivity of the organic thin film when the electric field was applied occurred because the polar functional group responded to the electric field, and the effect of the response spread to the structure of the conductive network.

Further, the conductivity can be further improved by incorporating a charge-transporting dopant substance into the conductive network by doping. As this dopant substance, any dopant substance such as iodine, BF- ion, alkali metal such as Na and K, and alkaline earth metal such as Ca can be used. Further, it may contain a trace component contained in the solution in the organic film forming step or a dopant substance due to contamination unavoidably mixed from a glass container or the like.

The organic molecules that make up the conductive monolayer are fairly well-aligned, so the conjugated chains of the conductive network are in a particular plane. Therefore, the conductive net formed on the monolayer is linearly connected in a predetermined direction. Due to the linearity of the conductive network, it has high conductive anisotropy. In addition, the linearity of the conductive network means that each conjugated bond chain (conjugated system) constituting the conductive network is arranged substantially in parallel on the same plane in the monolayer. Therefore, the conductive monolayer has high electrical conductivity and uniform electrical conductivity. In addition, due to the linearity of the conductive network, the monomolecular layer has a conjugated bond chain having a high degree of polymerization.

According to another example, it is possible to provide a conductive monomolecular film and a conductive monomolecular cumulative film having extremely good conductivity even if the film thickness is small.

In the case of a conductive monomolecular cumulative film, since a conductive network is formed in each conductive monolayer, the conductivity of the conductive network of the monomolecular cumulative film is It depends on the number of layers of the layered monomolecular film. Therefore, a conductive organic thin film having a desired conductivity can be provided by changing the number of stacked conductive monolayers. For example, in the case of a conductive cumulative film in which the same conductive monolayer is laminated, the conductivity of the conductive network included therein is approximately proportional.

In the conductive monomolecular cumulative film, the tilt angle of the orientation of the organic molecule may be different for each monolayer as long as the direction of the conductive network formed in all the monolayers is the same. Also, not all monolayers need to be composed of the same organic molecule. Further, a conductive monomolecular built-up film composed of different kinds of organic molecules for each conductive monomolecular layer may _t Also, in the case of the conductive monomolecular built-up film, the conductive closest to the substrate Since the water-soluble monolayer is chemically bonded to the base material, it has excellent durability such as peel resistance.

The tilt direction of the organic molecule in the tilting process means the direction of a line segment obtained by projecting the long axis of the organic molecule onto the substrate surface. Therefore, the inclination angles with respect to the substrate need not be the same.

The group of organic molecules constituting the monolayer can be accurately tilted in a predetermined direction in the tilting step. Generally, the molecules that make up the monolayer can be oriented. Since alignment can be performed with high accuracy, a conductive network having directionality can be easily formed in the conductive network forming step.

In addition, when the oriented organic molecules in the monolayer are conjugated to each other, a conductive network having a high degree of polymerization and being linearly connected can be formed. In addition, a uniform conductive monolayer can be formed due to the linearity of the conductive network. In another example, a polarized light having a wavelength in a visible light region is used as the polarized light. According to this example, it is possible to prevent or suppress the destruction of the organic thin film due to the exfoliation of the organic molecules constituting the organic thin film and the destruction of the organic molecules themselves. According to another example, when an organic thin film is formed on the surface of a rubbed substrate, the organic molecules constituting the organic thin film are inclined in a predetermined direction. Generally, the rubbing direction in the rubbing process is the same as the tilt direction of the formed organic molecules.

Nylon or rayon cloth can be used as the rubbing cloth used in the rubbing treatment. It is appropriate to use a rubbing cloth made of nylon or rayon as described above for the purpose of improving the accuracy of orientation.

In the conductive network forming step, one or more polymerization methods are applied, and molecules constituting the organic thin film are conjugated to each other by polymerization or by polymerization or a bridge after the polymerization to form a conductive network. Is also good. According to this example, it is possible to form a conductive network that enables electric conduction by connecting the polymerizable groups of the organic molecule by a conjugate bond. As the type of polymerization, at least one polymerization method selected from electrolytic oxidation polymerization, catalytic polymerization, and irradiation beam irradiation polymerization can be used. Particularly in the final step, when to complete the more conductive network in the electrolytic oxidation polymerization, also _c it is possible to obtain a high conductivity, if molecules forming the organic thin film has a plurality of polymerizable groups that bind with conjugated bonds, whereas By conducting a cross-linking reaction on the polymer formed by the polymerization of the polymerizable group to form a conjugate bond with the other polymerizable group, a conductive network having a structure different from the structure after the polymerization can be formed. At this time, the other polymerizable group on the side chain of the polymer formed by polymerization is bridged.

For example, when a monomolecular film composed of a group of organic molecules having a diacetylene group is formed, catalytic polymerization is performed on the monomolecular film, and crosslinking is performed by energy beam irradiation polymerization, an extremely high conductivity is obtained. A conductive network including a polyacene-type concomitant system can be formed. In the step of performing the polymerization, a polymerization method selected from the group consisting of a catalyst polymerization method, an electrolytic polymerization method, and an energy beam polymerization method may be applied. According to this example, a catalyst polymerization method is applied to an organic thin film composed of an organic molecule having a polymerizable group having catalytic polymerizability (hereinafter, also referred to as “catalyst polymerizable group”). An electropolymerization method is applied to an organic thin film composed of organic molecules having a polymerizable group (hereinafter abbreviated as an electropolymerizable group), and a polymerizable group polymerized by irradiation with an energy beam (hereinafter referred to as an energy beam). A conductive network can be formed by applying an energy beam polymerization method to an organic thin film made of an organic molecule having a polymerizable group. In order to efficiently form a conductive network, first, catalytic polymerization and no or energy beam polymerization are performed, and the reaction is completed by electrolytic oxidation polymerization in the final step.

When a plurality of cross-linking steps are employed, a combination of cross-linking steps by different actions may be used, but also includes a combination of steps having the same action but different reaction conditions. For example, a conductive network may be formed by performing a cross-linking step by irradiation of a first type of energy beam after a cross-linking step by catalytic action, and further by performing a cross-linking step by irradiation of a second type of energy beam. In the conductive network forming step, the catalytic polymerization method is applied as a polymerization method. Form a network.

For example, a conductive network including a polypyrrole-type conjugated system can be formed using an organic molecule including a pyrrole group, and a conductive network including a polychenylene-type conjugated system can be formed using an organic molecule including a chelenylene group. Applying the energy beam polymerization method in the conductive network forming step, and having an acetylene group or a diacetylene group as the polymerizable group. A conductive network may be formed on the organic thin film composed of a group of organic molecules. According to this example, a conductive network including a polyacetylene-type conjugated system can be formed by using an organic molecule having an acetylene group as an organic molecule constituting the organic thin film. In addition, a conductive network including a polydiacetylene-type conjugated system or a polyacene-type conjugated system can be formed using an organic molecule having a diacetylene group.

Ultraviolet rays, far ultraviolet rays, X-rays or electron beams may be used as the energy beam. According to this example, a conductive network can be efficiently formed. In addition, since the absorption characteristics differ depending on the type of polymerizable group irradiated with energy beam, the reaction efficiency can be improved by selecting the type and energy of the energy beam having good absorption efficiency. Furthermore, since many energy beam-irradiated polymerizable groups have absorbability to these energy beams, they can be applied to organic thin films composed of organic molecules having various types of beam-irradiated polymerizable groups.

Further, the tilting step and the conductive network forming step can be performed simultaneously by using polarized ultraviolet rays, polarized far ultraviolet rays or polarized X-rays as the energy beam. According to this example, the organic molecules constituting the organic thin film can be inclined (orientated) in a predetermined direction, and the organic molecules can be conjugated to each other. Therefore, the process can be simplified.

The substrate may be an electrically insulating substrate such as glass or a resin film, or a substrate with an insulating film in which an insulating film is formed on an arbitrary substrate surface. If the substrate is glass or polyimide resin, it has active hydrogen on the surface and can be used as it is. For the active hydrogen is less _{_{substrate, SiCl 4, HSiCl 3, SiCl}} 3 0- (SiCl 2 - 0) n - SiCl 3 ( and伹, n represents an integer of 0 to 6), S i (0CH ₃₎ _{4, HSi (OCH3) 3,} Si (OCH3) 3O- (S i (0CH 3) 2 - 0) n -S i (0CH 3) 3 ( where, (n is an integer of 0 or more and 6 or less). Active hydrogen can be provided by treating the substrate surface with a silica film, corona discharge, plasma irradiation, or the like.

When the substrate is an electrically insulating material, an organic electronic device having a small leakage current and excellent operation stability can be provided.

The organic conductive film of the present invention has high conductivity and high transparency. Applications that take advantage of this property include wires, motors, generators, capacitors (capacitors), transparent electrodes (alternative to ITO), semiconductor device wiring, CPU wiring (no heat generation due to electrical resistance), electromagnetic shielding, CRT Various applications such as glass surface filters (prevention of static electricity generation) are possible.

(Embodiment 1)

In the first embodiment, a method for manufacturing the organic thin film and a structure thereof will be described taking a case where the organic thin film is a monomolecular film as an example.

First, the manufacturing method will be described. An organic molecule having a conjugated polymerizable functional group is brought into contact with a base material to perform a monomolecular layer forming step (organic thin film forming step) for forming a monomolecular film on the base material. Region forming step of forming a conductive region having a conductive network in which molecules that are connected to each other in a predetermined direction by covalent bonding is formed in at least a part of the single-molecule film, whereby a monomolecular film having a conductive region can be formed. .

In order to form a conductive network having better directionality than the conductive network formed by the above-described manufacturing method, the organic molecule constituting the film must be oriented (inclined) in a predetermined direction with respect to a monomolecular film. It is preferable to perform a conductive region forming step. In addition, when the conductive region forming step is performed on the oriented monomolecular film, a conductive region having a high degree of polymerization and high conductivity can be formed. Here, in monolayers and monolayers, tilting in a predetermined direction is equivalent to orienting the organic molecules constituting the monolayer. In the following, a monolayer or a monolayer is also referred to as an orientation.

As a method for forming such an oriented monomolecular film, a rubbing treatment is performed on the substrate surface before the monomolecular layer forming step (pretreatment step), and the monomolecular film is formed on the rubbed substrate surface. A method of forming the monomolecular film, a method of performing an orientation treatment on the monomolecular film after the monomolecular layer forming step (gradient treatment step), and forming an oriented monomolecular film can be applied. In addition, if the manufacturing method includes a pretreatment step and a tilt treatment step, a conductive network having extremely excellent linearity can be formed.

If the manufacturing method includes a washing step following the above-mentioned monolayer formation step, a monomolecular film having no stain on the surface can be formed. Further, if the manufacturing method includes a doping step of doping a charge-transporting dopant, the conductivity of the conductive region can be easily improved. In addition, if the manufacturing method includes a step of forming an insulating protective film on the monomolecular film after the conductive region forming step, a monomolecular film with a protective film having excellent durability such as peel resistance can be manufactured. . Hereinafter, each step will be described.

In the monomolecular layer forming step, the monomolecular film may be formed by immersing the base material in an organic solution containing the film material molecules, or the monomolecular film may be formed by applying the organic solution onto the base material. You may. Alternatively, a monomolecular film may be formed by exposing the substrate to a gas containing film material molecules.

When an organic molecule having a functional group that chemically adsorbs to the substrate, such as a silane-based surfactant, at the terminal is used as a film material molecule, it has excellent durability such as peel resistance bonded and fixed on the substrate. A monomolecular film can be formed. In the case of forming a second or subsequent laminated film, a chemisorption method or a Langmuir-Blodgett method can be applied.

In addition, the monomolecular layer forming step may be a step of forming a monomolecular film on the entire surface or a part of the surface of the base material, or forming the monomolecular film on the base material in a predetermined pattern. Forming step. For example, a coating (resist pattern) is formed on a portion other than the pattern where a monomolecular film is formed on the surface of the base material, and the base material on which the coating is formed is brought into contact with the film material molecules to form a monomolecular film. After that, the coating is removed to form a monomolecular film in a predetermined pattern. Next, in the washing step, after the monomolecular layer forming step, the substrate on which the monomolecular film is formed is immersed in an organic solvent for washing, so that unadsorbed organic molecules can be washed and removed. It is preferable to use a non-aqueous organic solvent as the organic solvent for washing.

Next, the orientation treatment step may be a step of rubbing the surface of the base material in any one direction or a step of rubbing the rubbing direction so that the rubbing direction differs for each predetermined portion. Good. The rubbing treatment method will be described in the following inclination treatment step. The rubbing device used in the alignment process and the rubbing device used in the tilting process are the same device, and the difference is whether or not a monomolecular film is formed on the substrate (FIG. 5A). Hereinafter, an example of a pretreatment step in the case where the rubbing direction is made different for each predetermined portion will be described. A film is formed on the surface of the substrate in a predetermined first pattern (resist pattern), the surface of the substrate on which no film is formed is rubbed in a predetermined first rubbing direction, and the film is removed after the rubbing treatment. Thereafter, a coating (resist pattern) is formed on the surface of the substrate in a second pattern different from the first pattern, and the surface of the substrate on which no coating is formed is rubbed in a predetermined second rubbing direction, After the rubbing treatment, the coating is removed. Thereby, a portion rubbed in the first rubbing direction and a portion rubbed in the second rubbing direction can be formed. Further, by repeating this with different rubbing directions, a complicated rubbing pattern can be formed.

Next, the rubbing alignment method and the photo alignment The organic molecules constituting the monomolecular film can be oriented in a predetermined direction by applying a method, a liquid draining orientation method, or the like. 5A to 5C are schematic perspective views for explaining an orientation method for tilting (orienting) the molecules constituting the organic thin film, FIG. 5A is a rubbing orientation method, FIG. Figure 5C shows the draining orientation method.

In the rubbing orientation method, as shown in FIG. 5A, a rubbing cloth 4 which comes into contact with the monomolecular film 4 while transporting the substrate 1 on which the monomolecular film 4 is formed in a predetermined direction (substrate transport direction) C. The rubbing roll 4 wound around 1 is rotated in the rotation direction A, and the surface of the monomolecular film 4 is rubbed with the rubbing cloth 4 1 to rub the organic molecules constituting the monomolecular film 4. This is a method of orienting in the direction B. As a result, a monomolecular film oriented in the rubbing direction B on the substrate 1

4 can be formed.

As shown in FIG. 5B, the light alignment method uses a polarizing plate 4 having a transmission axis direction D.

3 is a method of irradiating ultraviolet light or visible light 45 onto the organic molecules constituting the monomolecular film 4 in the polarization direction E using the polarized light 46. Linearly polarized light is preferable as the polarized light. Thereby, the monomolecular film 4 oriented in the polarization direction can be formed on the substrate 1.

In addition, the draining orientation method uses an organic solvent for washing, as shown in Figure 5C.

In this method, the base material 1 is pulled up in the pulling direction F while maintaining a predetermined inclination angle with respect to the liquid surface of No. 4, and the organic molecules constituting the monomolecular film 4 are oriented in the draining direction G. Thus, an oriented monomolecular film 4 can be formed on the substrate 1.

Further, although not shown, the orientation can be achieved by the fluctuation of molecules in the solution at the time of catalytic polymerization or electrolytic oxidation polymerization.

Even if it is a process to apply any one of the draining alignment method, the rubbing alignment method, the photo alignment method, and the alignment due to the fluctuation of molecules in the solution during polymerization It is also possible to use a rubbing direction and a rubbing direction when forming an oriented monomolecular film in an accurately aligned state by combining different orientation methods. It is preferable that the polarization direction and the draining direction are the same.

In addition, the step may be a step of totally or partially orienting the monomolecular film in one direction, or a step of orienting the monomolecular film by changing the orientation direction for each predetermined portion. When the alignment direction is made different for each predetermined portion, it is preferable to apply a rubbing alignment method or a photo alignment method. By applying a rubbing alignment method, the alignment direction can be made different for each predetermined portion.

In addition, in the case where the alignment is performed with a different alignment direction for each predetermined portion by applying the optical alignment method, for example, the first polarized light is irradiated through a first photomask on which a predetermined pattern is formed. After that, a second polarized light having a polarization direction different from that of the first polarized light is irradiated through a second photomask having a predetermined pattern different from the pattern of the first photomask. I just need to. Furthermore, a complex alignment pattern can be formed by using a plurality of photomasks having different patterns and a plurality of types of polarization having different polarization directions.

If the monomolecular film is scanned and irradiated with polarized light while changing the polarization direction, not only a linearly connected conductive network but also a curved conductive network can be formed.

Next, in the conductive region forming step, the molecules constituting the monomolecular film can be polymerized or cross-linked to form a conjugated system. Catalytic polymerization, electrolytic polymerization, energy beam irradiation polymerization, and the like can be applied as polymerization methods for performing polymerization and cross-linking.

The conductive network may be formed by performing the step of polymerizing or crosslinking a plurality of times. For example, a conjugated polymerizable functional group (co- In the case where an organic molecule having a plurality of polymerizable functional groups polymerized by a minor bond) is used, a conjugate system (conjugate bond chain) can be formed on each of a plurality of parallel planes included in the monomolecular layer.

Further, when performing polymerization or crosslinking a plurality of times, the polymerization method or polymerization conditions may be different for each time. Here, the polymerization conditions refer to reaction conditions when the same polymerization method is used. For example, when the type of catalyst and the reaction temperature are different in catalytic polymerization, when the applied voltage is different in electrolytic polymerization, and when the energy beam irradiation polymerization is performed, the type of beam ゃ beam energy and beam irradiation intensity are used. Etc. are different.

Further, the step may be a step of forming a conductive region in all or a part of the monomolecular film, or a step of forming a plurality of conductive regions electrically insulated from each other in the monomolecular film. The case where the conjugated polymerizable functional group contained in the film material molecule is a catalyst polymerizable functional group, an electrolytic polymerizable functional group, or an energy-one beam irradiation polymerizable functional group will be described below.

First, the case where the organic molecule constituting the monomolecular film has a catalytic polymerizable functional group will be described. A conductive network can be formed by bringing the monomolecular film into contact with the catalyst. Therefore, the monolayer may be immersed in the solution containing the catalyst, the solution containing the catalyst may be applied to the monolayer, or the monolayer may be exposed to a gas atmosphere containing the catalyst. Alternatively, a gas containing a catalyst may be sprayed on the monomolecular film.

When the orientation treatment step (gradient treatment step) is not performed, a solution containing a catalyst is caused to flow in a certain direction with respect to the surface of the monomolecular film, or a gas containing a catalyst is supplied to the surface of the monomolecular film. By spraying in a certain direction, it is possible to orient the monomolecular film and to form a conductive network. Therefore, a conductive region including a conductive network connected in a predetermined direction can be formed by omitting the alignment process. Also, when forming a plurality of conductive regions that are electrically insulated from each other, a coating (resist pattern) having a predetermined pattern is formed on the monomolecular film, and then the coating is not formed by contacting with a catalyst. A conductive region can be formed at the site. If unnecessary, the coating may be removed.

Second, the case where the organic molecules constituting the monomolecular film have an electropolymerizable functional group will be described. By bringing a pair of electrodes having a potential difference into contact with the monomolecular film, a conductive network connected in a predetermined direction can be formed. Therefore, a pair of electrodes for electropolymerization that are in contact with the surface or side surface of the monomolecular film and are separated from each other may be formed, and a voltage may be applied between the pair of formed electrodes. A pair of external electrodes may be brought into contact with the surface or side surface of the molecular film so that the electrodes are separated from each other, and a voltage may be applied between the pair of external electrodes.

In the case of forming a plurality of conductive regions that are electrically insulated from each other, a plurality of pairs of electrodes are formed in a predetermined pattern, and a predetermined potential is applied to the electrodes so that the conductive regions are formed between electrodes having different potentials. Can be formed. At this time, a conductive region may be formed one by one by applying a potential to only two electrodes, or a plurality of conductive regions may be formed simultaneously by applying a potential to three or more electrodes. When an electrode is formed and electrolytic polymerization is performed, a monomolecular film having a conductive region with terminals can be manufactured. If unnecessary, these electrodes are removed. Thirdly, a case where the organic molecules constituting the monomolecular film have a polymerizable functional group irradiated with an energy beam will be described. By irradiating the monomolecular film with an energy beam, a conductive network can be formed. Light, X-rays, electron beams and the like can be used as the energy beam. Preferably, polarized or polarized X-rays are used as the energy beam.

Further, even when the alignment treatment step (tilt treatment step) is not performed, the monomolecular film can be oriented and a conductive network can be formed by irradiating polarized light. Therefore, the alignment process is omitted. Thus, a conductive region including a conductive network connected in a predetermined direction can be formed.

In the case where a plurality of conductive regions which are electrically insulated from each other are formed, an energy beam is irradiated through a first photomask in which a predetermined pattern is formed, and then a pattern of the first photomask is formed. An energy beam is irradiated through a second photomask having a different predetermined pattern.

At this time, the energy beam irradiated through the first photomask and the energy beam irradiated through the second photomask may not be the same energy beam. Furthermore, when polarized light or polarized X-rays are used as the energy beam, their polarization directions need not be the same. <For example, a plurality of photomasks with different patterns and a plurality of different polarizations with different polarization directions are used. By using, conductive regions having different conductive network directions can be easily formed.

Further, when the monomolecular film is scanned and irradiated with the energy beam, a plurality of conductive regions electrically insulated from each other can be formed more easily. At this time, if polarized light or polarized X-rays are used as the energy beam, conductive regions in which the directions of the conductive networks are different from each other can be easily formed. Furthermore, if scanning irradiation is performed while maintaining the polarization direction and the scanning direction (the direction of travel of the energy beam) in parallel, it is possible to form a conductive network that is curved and continues in a predetermined direction.

In order to efficiently form the conductive network, there is a method of first performing catalytic polymerization and polymerization by irradiation with a laser beam or a light energy beam, and finally completing the network by electrolytic oxidation polymerization. Catalytic polymerization and / or polymerization by light energy beam irradiation have a high polymerization rate, and electrolytic oxidation polymerization is not so fast, but polymerization is carried out while passing an electric current. Since a large current flows at the moment when the network is completed, it is easy to detect whether or not the network is completed.

Next, in the doping step, the conductivity can be easily improved by doping with a charge-transporting dopant. The dopant may be an x-ray dopant (electron acceptor) such as iodine (I ₂ ) or BF- ion, or a donor or electron donor (electron donor) such as Li. It may be.

Next, in a base material insulating film forming step, an insulating film such as a silica film or an aluminum oxide film can be formed on the substrate. For use as a transparent electrode or the like, it is necessary to form a transparent film. Further, when a film constituting molecules is formed as a chemisorbent film as an insulating film, a monomolecular film can be formed irrespective of the material of the base material.

Finally, in the protective film forming step, an insulating protective film is formed on the monomolecular film surface. By performing the protective film forming step, a monomolecular film having excellent durability such as peel resistance can be formed. Further, if the monomolecular film contains a dopant, evaporation of the dopant due to undoping can be reduced. For use as a transparent electrode or the like, a transparent protective film is formed.

FIGS. 1A to 1C show examples of the structure of a monomolecular film having a conductive region formed by the above-described manufacturing method. 1A to 1C are cross-sectional views schematically showing a monomolecular film having a conductive region formed on a base material. In FIG. 1A, a monomolecular film 4 is immobilized on the surface of a base material 1 by covalent bonds, a conjugate polymerizable functional group 9 is superimposed to form a conductive region 6 over the entire region, and a conductive network 5 is formed. Indicates that the device is being used. FIG. 1B shows a monomolecular film in which the conductive network 5 is formed in a plurality of partial regions (conductive regions 6, 6). FIG. 1C shows a monomolecular film composed of an organic molecule having a conjugated polymerizable functional group therein and having a conductive network formed in a plurality of partial regions (conductive region 6). FIG. 2 is a schematic plan view for explaining the direction of the conductive network 5 in the monomolecular film 4. In drawings other than FIG. 2, the meandering conductive network is represented as a straight line without meandering or a curve without meandering.

3A to 3D show examples of the pattern of the conductive region in the monomolecular film having the conductive region. FIGS. 3A to 3D are plan views schematically showing a configuration example of a conductive region 6 of a monolayer including a conductive network formed on a base material. FIG. 3A shows a monolayer 4 in which a conductive network 5 extending in one direction is formed in the entire region, and FIG. 3B shows a parallel structure in which a conductive network 5 extending in one direction is formed in each conductive region 6. FIG. 3C shows a monolayer 4 having a matrix-shaped conductive region 6 in which a conductive network 6 connected to each conductive region in one direction is formed. FIG. 3D shows a monolayer having conductive regions 6 arranged in an arbitrary pattern in which the directions of the conductive networks formed in the conductive regions are not the same and the shapes of the conductive regions are not the same. 4 is shown.

FIGS. 4A and 4B show a structure of a monomolecular film having a conductive region formed over a base material. FIGS. 4A and 4B are cross-sectional views schematically showing examples of the structure of a monomolecular film formed on a base material. Fig. 4A shows a monomolecular film formed on the base material 1 with the base insulating film 2, and Fig. 4B shows a monomolecular film 4 formed on the base material 1 and having a protective film 3 formed on the surface. Is shown. Although not shown, a structure in which an insulating film, a monomolecular film, and a protective film are sequentially laminated on the base material from the base material surface may be used. FIG. 4 is a perspective view schematically showing a configuration example in which a conductive region is formed in a part. FIG. 6A shows a configuration in which a plurality of conductive regions 6 are formed in a monomolecular film 4 formed in all regions on the substrate 1, and FIG. 6B shows a configuration in which the conductive regions 6 are formed in all regions. The structure in which a plurality of monomolecular films 4 are formed on the substrate 1 is shown.

(Embodiment 2) In the second embodiment, an example of a monomolecular cumulative film having a conductive region will be described.

When forming a monomolecular built-up film, the first layer is _t second and subsequent layers formed by chemical adsorption method may be a chemical adsorption method, may be applied to Langmuir one Blodgett method. However, it is convenient and preferable to form a monomolecular multilayer film by a chemisorption method for all layers. Although the orientation treatment step (tilt treatment step) has been described in the first embodiment, the importance of the monomolecular accumulation film is greater than that of the monomolecular film. Hereinafter, a manufacturing method including an alignment treatment step will be described.

In the method for producing a monomolecular cumulative film having a conductive region according to the present invention, various combinations and orders of the monomolecular layer forming step, the conductive region forming step, and the alignment treatment step are possible. Hereinafter, preferred production methods are described in Production Methods 1 to 5.

Manufacturing method 1 is a method of forming a monomolecular cumulative film having a conductive region by performing a monomolecular layer forming process continuously plural times to form a monomolecular cumulative film and then performing a conductive region forming step. Is the way.

In the production method 2, the monomolecular layer forming step and the orientation treatment step (tilting treatment step) are sequentially and alternately performed a plurality of times to stack the oriented monomolecular layers, and then the conductive region forming step is performed. This is a manufacturing method for forming a monomolecular accumulation film having a conductive region.

Manufacturing method 3 is a manufacturing method of forming a monomolecular accumulation film having a conductive region by performing a series of steps of sequentially performing a monomolecular layer forming step, an orientation processing step (tilting processing step), and a conductive region forming step a plurality of times. It is.

Manufacturing method 4 includes a step of forming a monomolecular film having a conductive region by sequentially performing a monomolecular layer forming step, an orientation processing step (tilting processing step), and a conductive region forming step, and then repeating the monomolecular layer forming step a plurality of times. After that, the conductive region forming step This is a manufacturing method for forming a monomolecular cumulative film having a conductive region by performing the method.

Manufacturing method 5 is a method of forming a monomolecular accumulation film having a conductive region by performing a pretreatment step, successively performing a monomolecular layer forming step a plurality of times, and then performing a conductive region forming step. Is the way. Further, a manufacturing method in which any one of the manufacturing methods 1 to 5 is performed after the pretreatment step is performed is also preferable.

Even when the above-described manufacturing methods 1 to 5 are used, what kind of pattern of the conductive region is formed in the monomolecular cumulative film having the conductive region, and what kind of alignment method is used in the alignment processing step The superiority differs depending on the manufacturing method depending on the application method, the type of polymerization method used in the conductive region forming step, and the like. Therefore, it is important to select an optimal manufacturing method to form a monomolecular cumulative film having a desired conductive region.

The manufacturing methods 1 to 5 may be a manufacturing method including one or more of a base insulating film forming step, a cleaning step, a doping step, and a protective film forming step. Details of each of the monomolecular layer forming step, the conductive region forming step, the pretreatment step, the orientation step, the base insulating film forming step, the cleaning step, the doping step, and the protective film forming step are described in Embodiment 1 above. For reference, the differences between the respective steps that occur depending on whether the organic thin film is a monomolecular film or a monomolecular cumulative film will be described below.

In each monolayer formation step, the same film material molecule may be used to form a monomolecular cumulative film composed of one kind of organic molecule, or a different film material molecule may be used for each monolayer. A monomolecular cumulative film having different constituent molecules may be formed.

Next, the applicability of the rubbing alignment method and the photo alignment method in the alignment processing step will be described. Here, simply apply the Langmuir-Projet method. In the molecular layer formation step, the substrate is pulled up from the solution containing the film constituent molecules at a predetermined angle, usually perpendicular to the solution surface, so that the liquid is aligned in the single molecule formation step. become.

The rubbing orientation method is a method in which the organic molecules constituting the film are oriented by rubbing the surface of the film. The layers cannot be fully oriented. Therefore, the rubbing orientation is suitable when the production methods 2 to 4 are applied. When manufacturing method 1 is used to form a monomolecular cumulative film with a small number of laminated layers, the rubbing alignment method can be used.On the other hand, the photo-alignment method can be used for a monomolecular cumulative film with a large number of laminated layers. Therefore, it is suitable for any of the manufacturing methods 1 to 5. However, when the number of laminated layers is excessively large and the light transmittance is deteriorated, the lower monolayer on the substrate side cannot be sufficiently oriented.

Next, in the case where a catalytic polymerization method, an electrolytic polymerization method, or an energy beam irradiation polymerization method is applied in the conductive region forming step, a preferable production method will be described for each polymerization method.

Catalytic polymerization is a method of inducing a polymerization reaction by bringing the surface of a monomolecular accumulation film into contact with a catalyst, so that a sufficiently polymerized conductive network can be formed in the lower monolayer on the substrate side. It will be difficult. Therefore, when the catalytic polymerization method is applied, the above production method 4 is suitable. In the case of forming a monomolecular cumulative film having a very small number of laminations, the manufacturing method 1 or the manufacturing method 2 may be used.

Also, when applying the electrolytic polymerization method, it is difficult to form a sufficiently polymerized conductive network in the lower monolayer on the substrate side when a voltage is applied to a pair of electrodes in contact with the surface of the monomolecular accumulation film. Therefore, it is preferable to apply a voltage to the electrode in contact with the side surface of the monomolecular accumulation film. Thus, the side If a voltage is applied to the electrode in contact with the portion, a conductive network can be formed in each monolayer of the monomolecular accumulation film by applying any of the above-mentioned production methods 1 to 5. Further, the electrolytic polymerization method is suitable for forming a conductive region on the entire surface of the monomolecular accumulation film or for forming a conductive region penetrating the monomolecular accumulation film.

In addition, the energy beam irradiation polymerization method can be applied to a monomolecular cumulative film having a large number of stacked layers, and thus is suitable for any of the manufacturing methods 1 to 5. In the case where the permeability of the polymer is deteriorated, the lower monolayer on the substrate side cannot be sufficiently oriented.

Next, the washing step is preferably performed only after the formation of the lowermost monolayer on the substrate side. This is because if the cleaning step is performed after laminating the monomolecular layers, the laminated monomolecular layers are peeled off. When the lowermost monolayer is formed by applying the chemisorption method, it is preferable to perform the washing step.

Next, the doping step is preferably performed individually on the monolayer on which the conductive network is formed. Therefore, when performing the doping step, it is preferable to apply the manufacturing method 3, and it is preferable that the doping step is performed after each conductive region forming step of the manufacturing method 3.

FIGS. 7A to 7D show examples of the structure of the conductive region of the monomolecular cumulative film formed by the above-described manufacturing method. In addition, the pattern of the conductive region of each monolayer of the monomolecular cumulative film having the conductive region is all FIGS. 7A to 7D are cross-sectional views schematically showing an example of a laminated structure of a monomolecular cumulative film formed on the base material 1. 7A shows an X-type monomolecular accumulation film in which the orientation direction of each monolayer 4 is the same direction, and FIG. 7B shows a Y-type monomolecular accumulation film in which the orientation direction of each monolayer 4 is the same direction. Fig. 7C is an X-type monomolecular cumulative film in which the orientation direction is different for each monolayer 4, and Fig. 7D is It is an X-type monomolecular cumulative film oriented in one of two orientation directions for each sublayer 4.

Further, a structure having a monomolecular accumulation film can be used instead of the monomolecular film in FIGS.

(Embodiment 3)

The electric cable according to the present embodiment will be described with reference to FIGS. FIGS. 8A to 8C are diagrams schematically showing an example of a structure of an electric cable using a conductive region on which a monomolecular film is formed as a core wire. FIG. 8A shows an electric wire having a conductive monomolecular film 6 formed on the outer surface of a core wire 11 made of glass or metal and having the entire region as a conductive region, the surface of which is covered with an electrically insulating film 13. It is sectional drawing of a cable. Fig. 8B shows a collective wire type including a monomolecular film 4 having four conductive regions formed on the surface of a square pillar-shaped insulating substrate 11 and having an outer surface coated with an insulating protective film 13. the _c-diagram 8 C is a perspective view of an electrical cable, formed on the substrate, the collection electrodes type Furattoke one table that includes a contact 7 of the monomolecular film 4 and the four pairs of the conductive region 6 the whole area FIG. The flat cable in FIG. 8C is a flat cable having four core wires because the conductive region of the organic thin film has high conductivity anisotropy.

Also, by forming an insulating protective film on the organic thin film 4 having the conductive region 6 on the insulating base material 1 shown in FIGS. A flat cable can be provided.

(Embodiment 4)

The organic thin film of the present invention can provide various devices used as a conductive wire, a collective wiring, an electrode, and a transparent electrode. For example, electronic devices such as semiconductor elements, capacitors, and semiconductor devices, and optical devices such as liquid crystal display devices, electroluminescent devices, and solar cells can be provided. For example, FIGS. 9A and 9B are cross-sectional views schematically showing an example of the structure of a capacitor using a conductive region formed on a monomolecular film as an electrode. FIG. 9A is a sectional view showing a monomolecular film 4 having a conductive region 6. In this structure, the dielectric material 8 is sandwiched between the two base materials 1 with each monomolecular film 4 inside, and FIG. 9B shows the conductive material on each of the two parallel surfaces of the dielectric material 8. This is a structure in which a monomolecular film 4 having a region 6 is formed. In FIG. 9A and FIG. 9B, when a metal contact 7 (wiring, lead wire) penetrating the conductive region 6 is formed in a direction orthogonal to the direction of the conductive network, a uniform voltage is applied to the entire surface of the organic thin film electrode. Applicable and preferred.

The pyrrole compound of the present invention is obtained, for example, by reacting pyrrole with terminal bromo 1-alkyl to synthesize 1-pyrrolylalkyl, and by reacting the synthesized 1-pyrrolylalkyl with trichlorosilane. , 11-Pyrrolylalkyltrichlorosilane can be synthesized. In the case of alkyl-1-pyrrolylalkyltrichlorosilane, for example, a step of reacting alkylpyrrole with terminal bromo-1-alkyl to synthesize alkyl-1-pyrrolylalkyl, and the above-mentioned synthesized alkyl-1-pyrrolylalkyl and trichlorosilane Can be synthesized by reacting Chenyl compounds can be similarly synthesized.

(Example)

Hereinafter, the present invention will be specifically described based on examples. In the following examples, simply expressing% means mass%.

(Example 1)

[1] Synthetic process 1. Synthesis of 1 1- (1-pyrrolyl) -11-pandecene According to the reaction formula 1 shown in the following chemical formula (E), pyrrole 38.0 g (0.56 7 mol) and 200 ml of dehydrated tetrahydrofuran (THF) were charged and cooled to 5 ° C or lower. To this, 354 ml (0, 567 mol) of a 1.6 M n-butyllithium hexane solution was added dropwise at 10 ° C or lower. After stirring at the same temperature for 1 hour, 600 ml of dimethyl sulfoxide was added, and THF was distilled off by heating to replace the solvent. Next, 145.2 g (0.623 ol) of 111-promodeonedecene was added dropwise at room temperature. After the addition, the mixture was stirred at the same temperature for 2 hours. Next, 60 Omol of water was added to the reaction mixture, hexane extraction was performed, and the organic layer was washed with water. After drying over anhydrous magnesium sulfate, the solvent was distilled off.

Further, the residue was purified by silica gel column with hexane / ethyl acetate = 50Z1 to obtain 11.2 g of 11- (11-pyrrolyl) -11-pinedecene.

Reaction formula 1.

Br- (CH ₂ ) _ir CH = CH ₂

Γ NH N-(CH „) _n -CH = CH,

(E) The yield was 91.2%.

Here, the 3-position of the pyrrolyl group was substituted with an alkyl group or an alkyl group represented by the following formula 12 (a) to (e) containing an unsaturated group such as a vinyl group or a ethynyl group at the terminal. Even when the raw materials were used, 11- (1-pyrrolyl) -1-dendene, in which the 3-position of the pyrrolyl group was alkylated or alkylated, was obtained.

(a) CH (CH _fi- (b) CH-(CH) ₇ —

(c) CH (CH J _fl —

(d) CH _? = CH— (CH?) _fi — (e) (CH ₃ ) 3 S i -C≡C- (CH ₂ ) ₆ —

[2] Synthetic process 2. Synthesis of 1 1- (1-pyrrolyl) 1-decenyltrichlorosilane

The reactions (1) to (8) were performed according to the reaction formula 2 shown in the following chemical formula (F). Conversely, the formula Δ.

(1) In a 50m 1 cap pressure-resistant test tube, add 1 1- (1_pyrrolyl) 1-1-undecene 2.0 g, (9.1 x 10-½ol), trichlorosilane 2.0 g (1.48 x 10— ² mol) and AIBN (0.015 g) were charged and reacted at 80 for 5 hours.

Thereafter, it was reacted checked by NMR, _c further trichlorosilane was nearly unreacted 2. 0 g (1. 4 8 X 1 0 - 2 mol), AIBN

0.015 g was added and reacted at 100 ° C. for 22 hours. When the reaction was checked, about 50% of the reaction had progressed.

(2) to 5 Om 1 capped pressure tube, 1 1 _ (1 one pyrrolyl) Single 1 one Undesen 2.0 g (9. 1 X 1 0- 3 mol), trichlorosilane 2. 0 g (1.48 X 1 0 ^{_{"2 ol), H 2 PtCl}} 6 · 6H 2 0 to 5% isopropyl alcohol solution 0.0 1 g was 9 hours at charging 50 ° C in. was reacted Ji Eck at negation R, about 50% The reaction was in progress.

Thereafter, the reaction was carried out overnight at the same temperature, but the reaction did not proceed.

(3) In a 3 Om1 reaction vessel equipped with a reflux condenser and a dropping funnel, 1 1 - (1 one-pyrrolyl) _ 1 one Undesen 2. charged 0 g (9. 1 X 1 0 -¾ol), 5% isopropyl alcohol solution 0.0 1 g of _{_{_{H 2 PtCl 6 · 6H 2 0}}} , to 7 0 ° C Heated. To this was added dropwise trichlorosilane 1.49 g of (1 0 X 1 0 one ² mol) over a period of 2 hours at 60 to 70 ° C.

Thereafter, the reaction was carried out at the same temperature for 2 hours.

When checking the reaction with the bandit R, the reaction was progressing about 50%. Thereafter, the reaction was carried out overnight at the same temperature, but the reaction did not proceed.

(4) In a 50 m1 reaction vessel equipped with a reflux condenser and a dropping funnel, 1 1 1 (1 -pyrrolyl) 1 1-pendene l O. O g (4.57 X 10-2 mol), H 0.05 g of a 5% isopropyl alcohol solution of ₂ PtCl 6 H ₂₀ was charged and heated to 70 ° C. This trichlorosilane 7.45 g (5.5 0 X 1 0- 2 mol) of 60-7 0: was added dropwise over 4 hours.

Thereafter, the reaction was carried out at the same temperature for 6 hours. When the reaction was checked by NMR, it was found that the reaction had progressed by about 50%.

Thereafter, 0.05 g of a 5% isopropyl alcohol solution of H ₂ PtCl 6H _{20 was} added and reacted overnight at the same temperature, but the reaction did not proceed.

To this was added dropwise over 2 hours at trichlorosilane 7.45 g (5. 50 X 1 0 "2 ιο1) a 6 0~ 7 0 ° C. At this time, in order to trichlorosilane reflux temperature 5 0 ° C After dropping, the mixture was allowed to react for 6 hours, and when the reaction was checked, the reaction did not proceed.

This was transferred to a 50 ml pressure-resistant test tube with a cap, and reacted at 100 ° C. overnight, but there was no change.

This was distilled under reduced pressure to obtain 4.0 g of 111- (1-1-pyrrolyl) -pentadecenyltrichlorosilane.

At this time, the bp of the obtained substance was 119 to 121 / 5.32 Pa (0.0 imHg), and the yield was 24.7%. (5) In a 50m1 pressure-resistant test tube with a cap, add 1- (1-pyrrolyl) -111-decene 10.Og (4.57 X10 "½ο1) and trichlorosilane 10.0 g (7. ^{3 8 X 1 0- 2 mol)} , was hand checking the reaction to H ₂ PtCl ₆ · 6H ₂ 0 5% isopropyl alcohol solution 0.0 5 g of reacted for 3 hours at charging 1 0 0 ° C. NMR, 50 The reaction was continued overnight at the same temperature, but the reaction did not proceed.

(6) a reflux condenser, a 5 Om 1 reactor equipped with a dropping funnel, 1 1 - (1 one-pyrrolyl) _ l- Undesen 6 7. 0 g (3. 0 6 X 1 0 - 1 mol), H _{_{_{2 PtCl 6 · 6H 2 0 5}}} % isopropyl alcohol solution 0.34 g narrows specification was heated to 70 ° C. To this, 50.0 g (3.69 X 10-) ο1) of trichlorosilane was added dropwise at 60 to 70 ° C over 2 hours. Thereafter, the reaction was carried out at the same temperature for 3 hours. When the reaction was checked by NMR, it was found that the reaction had progressed by about 40%. After that, the reaction was continued overnight at the same temperature, but the reaction did not proceed.

The above (5) and (6) were combined and distilled under reduced pressure to obtain 26.9 g of 11- (1-piperyl) -p-decenyltrichlorosilane. At this time, the bp of the obtained substance is 121 to 123. /6.65 Pa (0.05 minHg), and the yield was 21.6%.

(7) a reflux condenser, a 5 Om l reactor equipped with a dropping funnel, 1 1 i (1-pyrrolyl) Single 1 _ Undesen 8 0. 0 g (3. 6 5 X 1 0 - 1 mol), H _{_{_{2 PtCl 6 · 6H 2 0 5}}} % isopropyl alcohol solution 0.4 1 g to narrow specifications and heated to 7 0 ° C. To this, 60.0 g (4.42 X 10-½ο1) of trichlorosilane was added dropwise at 60 to 70 over 2 hours. Thereafter, the reaction was carried out overnight at the same temperature. When the reaction was checked by NMR, it was found that the reaction had progressed by about 30%.

This was distilled under reduced pressure to obtain 17.0 g of 1 1 1 (1 pyrrolyl) Cenyltrichlorosilane was obtained. At this time, a the bp of the resulting substance 1 29~ 1 V / 3 3. 2 5Pa (0. 2 5mmHg), c (8) yield of 1 3.1% with 1 0 Om 1 cap In a pressure test tube, add 1 1 — (1-pyrrolyl) _ 1-dundene 45.0 g (2.05 X10-½ο1) and trichlorosilane 2 5.Og (1.85 X10) -½01), was reacted checked by H _₂ PtCl ₆ · 6H ₂ 0 to 5% isopropyl alcohol solution 0. 2 3 g charge 1 0 0 ° was reacted for 1 2 hour at C _c NMR, 5 0% The reaction was progressing to some extent.

This was distilled under reduced pressure to obtain 14.7 g of 11- (1-pyrrolyl) undecenyltrichlorosilane. At this time, a the bp of the resulting substance 1 24~ 1 2 5 ° C / 1 3. 3Pa (0. ImmHg), yields 2 2. Note _c was 4%, the reaction being (7) In (8), a reaction was performed using the recovered raw materials. As described above, eight kinds of synthesis conditions were examined as the synthesis method in the step 2, and all of the yields were about 20 to 25%. However, using the recovered raw materials, the trichlorosilane dropping method was as low as 13%. In addition, the drop rate seems to decrease the reaction rate as the scale increases.

From the above results, it is considered that the reaction condition (2) or (8) is appropriate considering the amount of the charge, the reaction time, and the like.

FIG. 17 shows an NMR chart of the obtained product, and FIG. 18 shows an IR chart thereof. NMR is used manufactured by JEOL Ltd. AL 3 0 0 (3 0 0 H z), were determined by dissolving the sample ₃ Omg CD C 1 3. The IR was measured by a neat method (measuring a sample between two pieces of NaC1) using A-100 manufactured by JASCO Corporation.

Here, the alkylation obtained in the synthesis step 1 in which the 3-position of the pyrrolyl group is substituted with an alkyl group or an alkyl group containing an unsaturated group such as a vinyl group or a acetylene group at the terminal, or 1 1— (1-Pyrrolyl) one-decene is used as a raw material, but alkylation or alkylation Fluorinated 11- (1-pyrrolyl) -p-decenyltrichlorosilane was obtained, respectively.

After diluting 1- (1-1-pyrrolyl)-undecenyltrichlorosilane shown in the following chemical formula (G) obtained by the above-mentioned reaction formula 2 (chemical formula (F)) to 1% with a dehydrated dimethyl silicone solvent, the chemical An adsorbent was prepared.

. N- (CH ₂ ) _ir SiCI ₃

(G)

Further, as shown in FIG. 10A, an electrically insulating silica film 2 having a thickness of 0.5 zm was formed on the surface of an electrically insulating polyimide substrate 1 having a thickness of 0.2 mm in advance.

Next, the polyimide substrate 1 was immersed in a chemisorption solution to chemically adsorb chemisorbed molecules on the surface of the silica film 2 (monomolecular layer forming step). After the monolayer formation process, the polyimide substrate 1 was immersed in a black form solution to wash and remove unreacted film material molecules remaining on the polyimide substrate 1. As a result, a monomolecular film 14 having no stain was formed on the surface (FIG. 10A).

At this time, a large number of hydroxyl groups containing active hydrogen are present on the surface of the silica film 2 on the polyimide substrate 1, so that the hydroxyl groups and the one SiC1 bonding group of the chemisorbed molecule are covalently bonded by a dechlorination reaction. Thus, a monomolecular film 14 composed of chemisorbed molecules represented by the chemical formula (H) is formed. However, in the chemical formula (H), the case where all —S i C 1 bonding groups in the chemisorbed molecule reacted with the surface of the silica film 2 was shown, but at least one S i C 1 bonding group was reacted with the silica film. 2 It only needs to react with the surface.

Next, rubbing treatment was performed on the surface of the formed monomolecular film 14 using a rubbing device (FIG. 5A) used for producing a liquid crystal alignment film, and the chemisorbed molecules constituting the monomolecular film 14 were aligned. (Inclination process) (Fig. 10B). In the rubbing process, a rubbing roll 42 with a diameter of 7.0 cm wound with a rubbing cloth 41 made of rayon was used. Rubbing was performed under the conditions of a substrate running speed of 40 mm / s. At this time, the monomolecular film 24 was oriented (inclined) substantially parallel to the rubbing direction.

Next, a pair of platinum electrodes 17 having a length of 50 mm is formed on the surface of the monomolecular film 24 at a distance of 5 mm by vapor deposition, photolithography, and etching at room temperature. Electrolytic oxidative polymerization was performed by immersing in ultrapure water and applying a voltage of 8 V between a pair of platinum electrodes 17 for 6 hours (conductive region forming step). As a result, a conductive region 16 having a conductive network including a conductive polypyrrole-type conjugated system connected in a predetermined direction (rubbing direction) with the following chemical formula (I) as a polymerized unit is formed between a pair of platinum electrodes 17. (Conducting region forming step) (Fig. 10D).

The thickness of the obtained organic conductive film was about 2.0 nm, and the thickness of the polypyrrole portion was about 0.2 nm.

By applying a voltage of 8 V through an organic conductive film between the pair of platinum electrodes 17 A current of 1 mA was able to flow. Thus, even without doping with donors and Akusepu evening like impurities, the monomolecular film 3 4 Conductivity of the conductive network having a conductive region of about 1 0 ³ S Bruno cm.

Since the conductivity of the conductive region formed as described above is about 1Z10 to 1Z100 of a metal, if a monomolecular film 34 is laminated, a semiconductor element の a functional device such as a capacitor. It was at a level that could be used for wiring and electrodes. Further, since the monomolecular film 34 according to the present embodiment does not absorb light having a wavelength in the visible region, it can be used as a transparent electrode of a liquid crystal display element, an electroluminescent element, a solar cell, etc. Met.

Although the polyimide substrate 1 provided with the insulating silica film 2 on the surface is used in the above-described embodiment, the same conductive region can be obtained by using the polyimide substrate provided with the insulating aluminum oxide film on the surface. Was obtained. Even when a conductive aluminum substrate is used instead of a polyimide substrate, a monomolecular film having a similar conductive region can be formed by providing a silicon film on the surface of the substrate or oxidizing the surface of the substrate. Obtained.

Also, the rubbing orientation method was applied in the above-described tilting process of the present embodiment, but before the monomolecular layer forming process, a rubbing process was performed on the surface of the polyimide substrate provided with the silica film, and thereafter, the same method was used. If a monomolecular film is formed, a monomolecular film oriented in the rubbing direction can be formed, and then, if a conductive region is formed in a similar manner, a monomolecular film having a conductive region with similar conductive characteristics can be obtained. Was done.

Although the rubbing orientation method was applied in the tilting process of the present embodiment, as shown in FIG. 5B, even when ultraviolet light was irradiated through the polarizing plate 43, the chemical composition of the monomolecular film 14 was reduced. It is possible to form a monomolecular film 24 in which the adsorbed molecules 22 are oriented substantially parallel to the polarization direction (photo-alignment method). After that, if a conductive region is formed by the same method as described above, a conductive film having higher conductivity is obtained. Monolayer with region 3 4 was obtained. The light used in the photo-alignment method is not limited to the above-mentioned polarized ultraviolet light, and any light having a wavelength that can be absorbed by the monomolecular film 34 can be used.

In addition, in the above-described cleaning step of the present embodiment, when the polyimide substrate 1 is pulled up from the chloroform solution for cleaning, as shown in FIG. 5C, the surface of the polyimide substrate 1 is leveled with the chloroform solution 44 for cleaning. Even if the liquid is pulled up almost vertically and drained, a monomolecular film 24 in which the chemisorbed molecules 22 constituting the monomolecular film are oriented substantially parallel to the draining direction is formed. Law) I was able to. Thus, the cleaning step and the tilting step can be performed simultaneously. Moreover, subjected to Hikarihai countercurrent process in monolayer liquid was removed orientation treatment, then, when forming a conductive region in the same manner as described above, the monomolecular film 3 4 having a conductive region of the conductivity 1 0 ⁴ SZ cm was gotten.

(Example 2)

Using 3-hexyl-1-pyrroliloctadecenyltrichlorosilane represented by the following chemical formula (J), which was synthesized in the same manner as in Example 1, diluted to 1% with an organic solvent of dehydrated dimethyl silicone and chemisorbed. A liquid was prepared.

(J)

Then, thickness 0. 2 mm of insulating polyimide substrate 101 to a thickness 0. Of insulative (or glass or a conductive metal substrate) film, for example, silica force protective film or the A 1 ₂ 0 ₃ The protective film 102 was formed (Fig. 11

A)

Next, the silica film is immersed in the adsorption solution to chemically adsorb to the surface of the silica film, and the unreacted substance remaining on the surface is washed and removed with a black hole form. 103 was selectively formed (FIG. 11B). At this time, the surface of the substrate (silica film or the A 1 ₂ 0 ₃ film) The active hydrogen containing anhydride groups there are many, one S i C 1 groups of the material caused a hydroxyl group and desalted hydrogen reaction A monomolecular film 103 composed of molecules represented by the following chemical formula (K) covalently bonded to the substrate surface was formed.

Then, as shown in Fig. 11C, the rubbing device 104 used for the production of the liquid crystal alignment film was used, and the indentation depth was 0 with a rayon cloth 105 (YA-20- manufactured by Yoshikawa Kako Co., Ltd.). When rubbing is performed in the direction almost perpendicular to the electrode gap under the conditions of 3 mm, 11.7 mm in width, 11.7 mm in rotation, 1200 rotations, and table speed of 40 mmZ sec, the molecules constituting the monomolecular film are almost in the rubbing direction. A monomolecular film 103 ′ oriented in parallel was obtained (FIG. 11D). Next, a 50 mm long platinum electrode (source, drain electrode) 106, 106 ′ was formed on the monomolecular film surface by 5 mm. A pair was formed by vapor deposition at intervals, and a DC electric field of 8 V was applied between the electrodes in ultrapure water at room temperature (25 ° C) for 6 hours to perform electrolytic oxidation polymerization of the pyrrolyl group 107. As a result, the electrodes as shown in FIG. 11E and the following chemical formula (L) are connected by a conductive polypyrrolyl group 107 ′ (combination bonding group), and the conductivity at room temperature (25) is 4%. X 1 0 ³ S / cm (in this monomolecular film, in field application of 8 V, it was possible to flow a current of 4mA) conductive monomolecular film 108 was obtained (FIG. 1 1 F)

If a larger current capacity is required, the terminal alkyl group may be replaced with an unsaturated hydrocarbon group, for example, a Bier group or an acetylene group as shown by D or E in the above formula (12). After performing a chemical adsorption reaction using an organic substance, it is oxidized after polymerization or before polymerization to convert it into hydroxyl groups (〇H), and the process of accumulating the monolayer of the next layer in the —OH portion is repeated. By accumulating the monomolecular films, a conductive monomolecular accumulated film could be formed.

This conductivity is about 1Z10 to 1/1100 of that of metal, and when laminated, it is a level that can be used for wiring and electrodes of functional devices such as semiconductor devices and capacitors. In addition, this film is a monomolecular film, and its thickness is extremely thin at the nanometer level, so that it hardly absorbs light of the wavelength of visible light and transmits it. Therefore, it was at a level that could be used for transparent electrodes such as liquid crystal display elements, electroluminescent elements, and solar cells.

Here, when orienting the molecules constituting the monomolecular film, irradiation with ultraviolet rays 122 through the polarizing plate 121 (FIG. 12A) causes the molecular 123 constituting the monomolecular film to have almost the same polarization direction. A monomolecular film oriented in parallel was obtained, and then polymerized by the same method as described above to obtain a conductive monomolecular film having higher conductivity.

As long as the light used for photo-alignment has a wavelength that is absorbed by the monomolecular film, the photo-alignment can be performed using ultraviolet light or polarized light in the visible light region.

After the monolayer is formed, it is immersed again in chloroform, which is the cleaning solution 124, and the same cleaning is performed. Further, the substrate is pulled up and drained, whereby the molecules constituting the monolayer are drained. direction is obtained substantially monomolecular film 123 oriented in parallel ', then, the electrolytic oxidation polymerization result in a similar way, at room temperature (2 5 ° C) at 1 0 ⁴ S · cm conductive monomolecular film Obtained (Fig. 12B). In addition, when the step of lifting and raising the substrate and draining the liquid was performed before the optical alignment, the alignment was further improved.

Such a coating could also be used as a transparent electrode instead of a transparent electrode made of indium tin oxide alloy (ITO) used in electroluminescent devices (EL) and solar cells.

Further, a plurality of conductive conjugated bond group is oriented in a specific direction monomolecular film-like or monomolecular built-up film shaped coating the layer, the conductivity will create a 1 0 ³ S / cm or more coatings, the capacitor It could also be used as an electrode, wiring for a semiconductor IC chip, or an electromagnetic wave shielding film.

(Example 3)

As shown in FIG. 13, in Example 1, a Si substrate 131 (used as a gate electrode) was used instead of the polyimide substrate 101, and a silicon dioxide film (S i〇 ₂ ) 132 was formed instead of the protective film 102. Then, after forming a similar conductive monomolecular film 133, a similar process was performed except that a pair of platinum electrodes (used as source 134 and drain 135 electrodes, respectively) were formed at 5 xm intervals. A thin-film transistor (TFT) -type organic electronic device (three-terminal device) 136 with _two gate insulating films was fabricated (Fig. 13).

In this device, the TFT channel is composed of a polypyrrolyl group, which is a conjugated bonding group bonded at both ends to the source and drain electrodes, so that the mobility of the field effect is about 100 Ocm ² / V * S Hundreds or more of organic TFTs were easily obtained.

(Example 4)

As shown in Fig. 14, first, a large number of organic electronic devices are used as liquid crystal operation switches. Are arranged in a matrix in a matrix pattern. The side electrodes were connected by a source wiring and a gate wiring, respectively. A transparent electrode 143 was formed on the drain side electrode using an indium-tin-tin oxide alloy (ITO).

Next, a polyimide film was formed on the surface of the array substrate by an ordinary method, and rubbed to form an alignment film 4, thereby producing an array substrate 145.

On the other hand, in parallel, a group of RGB color elements 147 are arranged and arranged in a matrix on the surface of an acrylic substrate 146 to form a color filter, and a conductive transparent electrode 148 is formed on the front surface to form a color filter substrate 149. Produced.

Next, a polyimide film was formed on one surface of the color filter and rubbed to form an alignment film 144 '.

Next, the array substrate 145 on which the alignment film is formed and the color filter substrate 149 are overlapped so that the alignment films face each other, and the sealing portion is sandwiched with the epoxy adhesive 151 with the spacer 150 interposed therebetween. A liquid crystal cell was prepared in which the periphery was sealed and bonded at predetermined intervals.

Finally, inject and seal the TN-type liquid crystal 152, mount an IC chip incorporating peripheral circuits, install polarizing plates 153, 153 'before and after, and incorporate the backlight 154 to incorporate the TN-type liquid crystal. The display device 155 was manufactured (FIG. 14). Since this method does not require substrate heating in the manufacture of the array, it was possible to produce a sufficiently high-quality liquid crystal display device using a substrate having a low glass transition point (Tg) such as an acrylic substrate.

At this time, a surfactant containing a hydrocarbon group (for example, CH _3- (CH ₂ ) ₉ -Si-Cl ₃ ) is used as an insulating monomolecular film or an insulating monomolecular accumulation film in contact with the gate electrode of the organic electronic device. ) Was used to form a CH _3- (CH ₂ ) ₉ _Si (_0-) ₃ monolayer by chemisorption. In this case, the withstand voltage characteristics were significantly improved from 0.5 X 101 ^Q VZcm to 1 X 101 ^Q VZ cm. The peeling strength was about 1 tonne cm ² , and a highly reliable liquid crystal display device could be manufactured. In the fourth embodiment, a production example of a pot-gate type liquid crystal display device is described. However, the present invention can be applied to a top-gate type liquid crystal display device.

(Example 5)

As shown in FIG. 15, first, in order to use a large number of organic electronic devices as operation switches of the electroluminescent device, the same process as in Example 1 was carried out, and three terminals were formed on the surface of a polyethylene sulfone substrate (0.2 mm thick) 161. A plurality of 162 organic electronic devices were arranged and formed in a matrix, and the respective source-side and gate-side electrodes were connected by a source wiring and a gate wiring, respectively. Further, a transparent electrode 163 was formed on the drain-side electrode using an indium-tin-tin oxide alloy (ITO), thereby producing an array substrate 164.

Next, a hole transport layer 165 was deposited on the transparent electrode 163 connected to the drain of the three-terminal organic electronic device, and further a red light emitting layer 166 (2, 3, 7, 8, 12, 13, 17, 17) 18-Cetacetyl-2 1 H2 3 H-porphine Platinum (Π)) and green light-emitting layer 6 6 '(Tris (8-quinolinolato) aluminum aluminum) and blue light-emitting layer 166 "(4, 4' _ Bis (2,2-diphenylvinyl) biphenyl) was mask-deposited, and then an electron-transporting layer 167 was deposited on the entire surface. A cathode 168 (for example, an alloy of Mg and Ag, A 1 and Li) Alloy or a layer of LiF and A1 on the electron transport layer 167), and finally, mounting an IC chip incorporating peripheral circuits to produce an EL display device 169. (Figure 15).

With this method, it was not necessary to heat the substrate in the manufacture of the array, so an EL display device with sufficiently high image quality could be created even with a polyethersulfone substrate.

At this time, if an insulating film is formed on the gate electrode of the organic electronic device using the surfactant containing a hydrocarbon group used in Example 4, the withstand voltage characteristics will be 0.5. ^{X 1 0 1 G VZcm~ 1 X} 1 0 1. It has been improved to VZ cm. The peel resistance was about 1 ton / cm ² , and a highly reliable liquid crystal display device could be manufactured.

In the process of forming the electroluminescent films individually connected to the drains of the three-terminal organic electronic device, three types of electroluminescent films that emit red, blue, and green light, respectively, are formed to form the electroluminescent films. A color display device could be manufactured.

(Example 6)

The present embodiment relates to a monomolecular film having a conductive region including a conductive network formed by electrolytic polymerization.

A chemical formula (M) containing, in advance, a pyrrole group which is a conjugated polymerizable functional group (a functional group polymerized by a conjugate bond) and a trichlorosilyl group (one SiCl ₃ ) which reacts with active hydrogen at the molecular end. Using the chemically adsorbed molecules shown in (1) as membrane material molecules, the solution was diluted to 1% by weight with a dehydrated dimethyl silicone organic solvent to prepare a chemisorbed solution. In addition, an insulating silica film 2 was formed on the surface of the insulating polyimide substrate 1 in advance.

, — (CH ₂ ) ₁₀ —SiCI ₃

(M)

At this time, since many hydroxyl groups containing active hydrogen exist on the surface of the silica film 2 on the polyimide substrate 1, the hydroxyl groups and the Si The monomolecular film 14 composed of the chemisorbed molecule represented by the chemical formula 2 is formed by a covalent bond chemically bonded by a dechlorination reaction with the C 1 bonding group. However, in chemical formula N, the case where all the —SiC1 bonding groups in the chemisorbed molecule reacted with the surface of the silica film 2 was shown, but at least one —SiC1 bonding group in the chemisorbed molecule was on the surface of the silica force film 2 It just needs to react.

Next, rubbing treatment was performed on the surface of the formed monomolecular film 14 using a rubbing device (FIG. 5A) used for producing a liquid crystal alignment film, and the chemisorbed molecules constituting the monomolecular film 14 were aligned. (Inclination process) (Fig. 10B). In the rubbing process, a rubbing roll 42 with a diameter of 7.0 cm, around which a rubbing cloth 41 made of rayon was wound, was used. The indentation depth was 0.3 mm, the nip width was 1.1.7 mm, the number of rotations was 1200 rpm, and the table speed was small. Rubbing was performed under the conditions of substrate speed (substrate running speed) 40 mm / s. At this time, the monomolecular film 24 was oriented (inclined) substantially parallel to the rubbing direction.

Next, a pair of platinum electrodes 17 having a length of 50 mm is formed on the surface of the monomolecular film 24 at a distance of 5 mm by vapor deposition, photolithography, and etching at room temperature. Electrolytic polymerization was performed by immersing in ultrapure water and applying a voltage of 8 V between a pair of platinum electrodes 17 for 6 hours (conductive region forming step). As a result, a conductive region 6 having a conductive network containing a conductive polypyrrol-type conjugated system connected in a predetermined direction (rubbing direction) with the following chemical formula (O) as a polymerization unit is formed as a pair of platinum electrodes 17. It was formed in between (conductive region forming step) (Fig. 10D).

A current of 1 mA was able to flow between the pair of platinum electrodes 17 by applying a voltage of 8 V. Thus, impurities such as Donna one Ya Akuseputa doped Shinano Kutomo, conductive network Bok work conductivity of about 1 0 ³ monomolecular film to have a conductive region of the SZ cm 3 4 was obtained.

Since the conductivity of the conductive region formed as described above is about 1Z10 to 1/1100 of a metal, if a monomolecular film 34 is laminated, a semiconductor element の a functional device such as a capacitor. It was at a level that could be used for wiring and electrodes. Further, since the monomolecular film 34 according to the present embodiment does not absorb light having a wavelength in the visible region, it can be used as a transparent electrode of a liquid crystal display element, an electroluminescent element, a solar cell, etc. Met.

Further, the rubbing orientation method was applied in the tilting process of the present embodiment, but before the monomolecular layer forming process, a rubbing process was performed on the surface of the polyimide substrate provided with the silica film. If a monomolecular film is formed, a monomolecular film oriented in the rubbing direction can be formed, and then, if a conductive region is formed in a similar manner, a monomolecular film having a conductive region with similar conductive characteristics can be obtained. Was done.

Further, the rubbing orientation method was applied in the tilting process of the present embodiment, As shown in FIG. 5B, even when ultraviolet light is irradiated through the polarizing plate 43, the monomolecular film 24 in which the chemisorbed molecules 22 constituting the monomolecular film 14 are oriented substantially parallel to the polarization direction is formed. Thereafter, a conductive region was formed by the same method as described above, whereby a monomolecular film 34 having a conductive region having more excellent conductivity was obtained. In addition, the light used in the photo-alignment method is not limited to the above-described polarized ultraviolet ray, and any light having a wavelength that can be absorbed by the monomolecular film 34 can be used.

In addition, in the above-described cleaning step of the present embodiment, when the polyimide substrate 1 is pulled up from the chloroform solution for cleaning, as shown in FIG. 5C, the surface of the polyimide substrate 1 is brought to the liquid surface of the chloroform solution 44 for cleaning. Even if the liquid is pulled up almost vertically and drained, a monomolecular film 24 in which the chemisorbed molecules 22 constituting the monomolecular film are oriented substantially parallel to the draining direction is formed. Law) I was able to. Thus, the cleaning step and the tilting step can be performed simultaneously. Moreover, subjected to Hikarihai countercurrent process in monolayer liquid was removed orientation treatment, then, when forming a conductive region in the same manner as, the conductivity 1 0 ⁴ monomolecular film having a conductive region of the S / cm 3 4 was obtained.

(Example 7)

In the same manner as in Example 1, 111- (3-thenyl) -1-1-decene is synthesized according to the reaction formula represented by the following chemical formula (P), and then 11-1 3-Chenyl) 111-decenyltrichlorosilane was synthesized.

The 1 1 (3-thenyl) 1-decenyltrichlorosilane obtained in the above was diluted to 1% with a dehydrated dimethyl silicone solvent to prepare a chemisorption solution. A glass substrate having a thickness of about 3 mm was immersed in the chemisorption solution, and kept at room temperature for 3 hours to chemically adsorb chemisorbed molecules on the surface of the glass substrate (monomolecular layer forming step). After the monolayer formation step, the glass substrate was immersed in a black hole form solution to wash and remove the remaining unreacted film material molecules. As a result, a clean monomolecular film was formed on the surface.

Since a large number of hydroxyl groups containing active hydrogen are present on the surface of the glass substrate, these hydroxyl groups and the SiC1 bonding group of the chemisorbed molecule are chemically bonded by a dechlorination reaction to form a covalent bond. A monomolecular film composed of the chemisorbed molecules shown in (R) is formed. However, in the chemical formula (R), the case where all the S i C 1 bonding groups in the chemically adsorbed molecule reacted with the glass substrate surface was shown, but at least one _S i C 1 bonding group was reacted with the glass substrate. It only needs to react with the surface.

0-

/

π—r (CH ₂ ) _.r Si-0-

(} V

^S (R)

Next, a rubbing treatment is performed on the surface of the formed monomolecular film using a rubbing apparatus (FIG. 5A) used for producing a liquid crystal alignment film, and the chemically adsorbed molecules constituting the monomolecular film are aligned. (Inclination process step). In the rubbing process, a rubbing roll with a diameter of 7.0 cm wound with a rubbing cloth made of rayon was used. The indentation depth was 0.3 mm, the nip width was 1.1.7 mm, and the rotation speed was 1 2 Rubbing was performed under the conditions of 0 rotation 3, table speed (substrate traveling speed) 40 mm / s. At this time, the monomolecular film was oriented (inclined) substantially parallel to the rubbing direction.

Next, a pair of platinum electrodes having a length of 50 mm is formed on the surface of the monomolecular film at a distance of 5 mm by vacuum evaporation, photolithography, and etching, and then ultrapure at room temperature. Electrolytic oxidative polymerization was performed by immersing in water and applying a voltage of 8 V between a pair of platinum electrodes for 6 hours (conductive region forming step). As a result, a conductive region having a conductive network containing a conductive polypyrrole-type conjugated system connected in a predetermined direction (rubbing direction) with the following chemical formula (S) as a polymerization unit was formed between a pair of platinum electrodes ( Conductive region forming step).

The thickness of the obtained organic conductive film was about 2.0 nm, and the thickness of the polyphenylene portion was about 0.2 nm.

A current of 1 mA was able to flow by applying a voltage of 8 V through the organic conductive film between the pair of platinum electrodes. Thus, even without doping with non pure materials such as donor Ya Akuseputa, the conductivity of the conductive network is a monomolecular film was obtained having a conductive region of about 1 0 ³ SZ cm.

(Example 8)

The present embodiment relates to a monomolecular film having a conductive region including a conductive network formed by catalytic polymerization.

Previously, including acetylene groups (one C≡C _) is conjugated polymerizable functional groups, and trichlorosilyl groups that react with active hydrogen in the molecule end (one S i C 1 ₃₎ Using a chemisorbed molecule represented by the chemical formula (T), a chemisorption solution was prepared by diluting to 1% with an organic solvent of dehydrated dimethyl silicone. Further, after an insulating silica film was formed on the surface of the insulating polyimide substrate in advance, a rubbing treatment was performed on the surface of the silica film (pretreatment step) to form a rubbed polyimide substrate.

(CH ₃ ) ₃ Si-C≡C- (CH ₂ ) ₁₀ -SiCl ₃ (T)

Next, the rubbed polyimide substrate was immersed in a chemisorption solution to chemically adsorb chemisorbed molecules on the surface of the silica film (monomolecular layer forming step). After the monomolecular layer forming step, the rubbed polyimide substrate was removed. It was immersed in a black hole form solution to wash and remove unreacted film material molecules remaining on the polyimide substrate. As a result, a clean monomolecular film represented by the following chemical formula (U) was formed on the surface. (CH ₃ ) ₃ Si-C≡C- (CH ₂ ) _{1 ()} -Si (-0-) ₃ (U)

Since a rubbed polyimide substrate was used, the chemically adsorbed molecules constituting the formed monomolecular film were oriented in the rubbing direction.

Next, Ziegler. Natta catalyst (of 5 X 1 0 one ² mo 1 liter solution and tetrabutyl titanate tri E chill aluminum ^{2. 5 X 1 0 "2 mol} / l solution) of monolayer toluene solvent comprising The formed polyimide substrate was immersed to perform catalytic polymerization (a conductive region forming step), whereby a conductive net including a polyacetylene-type shared system connected in the rubbing direction represented by the following chemical formula (V) was obtained. Was formed.

Next, the conductive region was doped with iodine ions, which are charge-transporting substances. Thus, the conductivity is can form an electrically conductive region of about 1 0 ⁴ SZcm. When doping was not performed, the conductivity of a conductive region having a conductive network containing a polyacetylene-type conjugated system was such that it could not be used as a conductor such as a conductor or a wiring.

(Example 9)

The present embodiment is directed to a monomolecular film having a conductive region including a conductive network formed by energy beam irradiation polymerization.

Previously, the following chemical formula containing a diacetylene group which is conjugated polymerizable functional groups (one c≡c one c≡c I), and a trichlorosilyl group that reacts with active hydrogen molecule end (one S i C 1 ₃₎ ( Using the chemisorbed molecule shown in (W) as the membrane material molecule, the solution was prepared by diluting it to 1% with an organic solvent of dehydrated dimethyl silicone.

(CH ₃ ) ₃ Si_C≡C— C≡C—. ― SiCl ₃ (W)

A monomolecular film was formed in the same manner as in Example 8 except that a chemical adsorbent containing a diacetylene group was used (monomolecular layer forming step). Next, the surface of the monomolecular film was subjected to a rubbing treatment (inclination treatment step), and then the whole surface was irradiated with ultraviolet rays, which are energy beams, at an energy density of 100 mJZcm ² to perform energy irradiation polymerization (conductive film). Region forming step). As a result, a conductive region having a conductive network containing a polydiacetylene-type conjugated system represented by the following chemical formula (X) connected in the rubbing direction was formed.

(X)

In this embodiment, the organic molecule containing a group is used as the film material molecule C, but the molecule represented by the chemical formula 8 containing the acetylene group (_C≡C-I) is used as the film material molecule, Irradiation with an electron beam at 100 mJZ cm ² in a gas atmosphere resulted in a monomolecular film having a conductive region with almost the same conductivity.

(Example 10)

The present embodiment relates to a monomolecular film having a conductive region in which a conductive network is formed by a two-stage polymerization reaction by applying catalytic polymerization and energy beam irradiation polymerization.

When an organic molecule having a diacetylene group was used in the same manner as in Example 9, the monomolecular film having a conductive region having a conductive network containing a polydiacetylene-type conjugated system was further provided with an X-ray energy beam. Then, energy beam irradiation polymerization was performed to form a conductive region having a conductive network containing a polyacene-type conjugated system.

(Example 11)

The present embodiment relates to a monomolecular cumulative film having a conductive region including a conductive network formed by energy beam irradiation polymerization.

After the monolayer of the first layer was formed in the same manner as in Example 9, the monolayer formation process using the Langmuir-mouth jet method was performed twice consecutively to form a total of three monolayer films. did. At this time, a conductive network was formed collectively on each monolayer by irradiation with one energy beam. Thus, when an organic molecule having a diacetylene group is used as a film material molecule, a single molecule having a conductive region in which a polydiacetylene-type conductive network is formed is formed. A cumulative film could be manufactured, and when an organic molecule having an acetylene group was used as a film material molecule, a monomolecular cumulative film having a conductive region in which a polyacetylene-type conductive network was formed could be manufactured.

(Example 12)

The compound obtained in Example 1 was diluted with dehydrated dimethyl silicone solvent to 1% to prepare a chemisorption solution. A glass fiber having a diameter of 1 mm was immersed in this chemisorption solution at room temperature (25 ° C.) for 1 hour, and a dechlorination reaction was performed on the surface of the glass fiber to form a thin film. Next, the unreacted compound was washed away with non-aqueous chloroform. As a result, a hydrogen chloride reaction occurred between the hydroxyl group on one surface of the glass fiber and the chlorosilyl group (1 SiCl) of the compound, and a monomolecular film was formed.

Next, the glass fiber on which the monomolecular film was formed was immersed in a chloroform solution to be washed, and when the glass fiber was pulled out of the chloroform solution, the monofilament was oriented by draining in the length direction.

Next, a nickel thin film was formed by vapor deposition on a part of the end of the glass fiber.

Thereafter, in a pure aqueous solution, electrolysis of 5 V / cm was applied between the electrodes to cause electrolytic oxidation polymerization. The conditions of the electrolytic oxidation polymerization were a reaction temperature of 25 ° C. and a reaction time of 8 hours. As a result, a conductive network was formed by electrolytic polymerization, and the two electrodes were electrically connected. At this time, a conjugate bond is formed in a self-organizing manner along the direction of the electric field. When the polymerization is completely completed, the two electrodes are electrically connected by a conductive network. In this manner, a polypyrrole conjugated polymer film having a length of 10 mm was formed on the glass fiber along the axial direction of the glass fiber. The thickness of the organic thin film was about 2.0 nm, and the thickness of the polypyrrole portion was about 0.2 nm. The obtained organic conductive film was transparent under visible light. An electric cable was manufactured by forming an insulating film so as to cover the surface of the organic thin film thus obtained. Figure 8A shows a cross-sectional view of the obtained electric wire. In FIG. 8A, reference numeral 11 denotes a glass core wire, reference numeral 6 denotes a polypyrrol electrolytically oxidized polymer film, and reference numeral 13 denotes a coating insulating film made of a room-temperature-curable silicone rubber.

The obtained organic conductive film was analyzed using a commercially available atomic force microscope (AFM) (manufactured by Seiko Instruments Inc., SAP380 ON) in AFM-CITS mode, voltage: lmV, current: 160 n The conductivity p under the condition of A was p: 1 × 10 ³ S / cm at room temperature (25 ° C.) without doping.

Further, by doping with iodine ions, the conductivity / 0 became 1 × 10 ⁴ SZcm.

An electric cable was manufactured by forming an insulating film so as to cover the surface of the organic thin film thus obtained. Room temperature curing type silicone rubber was used for the covering insulating film.

In this embodiment, the electric cable may form a collective electric wire including a plurality of core wires electrically insulated from each other.

In addition, metal can be used in addition to glass for the core wire when making electric wires. In the case of metal, when an oxide is formed on the surface, a monomolecular film is easily formed.

(Example 13)

An experiment was performed on a device (liquid crystal display) using the conductive region of the monomolecular film described in Example 1 as a transparent electrode.

Amorphous silicon thin film transistors (TFTs) were formed in a matrix on the first substrate in advance, and predetermined wirings were formed to form a TFT array substrate. In addition, a color filter is placed on the second substrate in advance. In this manner, a color filter and a substrate on which was formed were prepared.

Then, usually, instead of I Njiumu tin oxide alloy formed on the surface of the color filter as a transparent electrode (I TO) film, through a silica film on the color filter surface of the color filter substrate, the conductivity 1 0 ² A monomolecular film having a conductive region of SZcm or more on the entire surface was formed.

Next, after forming a first alignment film on the TFT array substrate and a second alignment film on the color filter substrate, respectively, the first alignment film and the second alignment film are set inside and the TFT alignment film is formed. An array substrate and a color filter substrate were attached at an interval of 5 urn to produce an empty cell.

Finally, after injecting the liquid crystal into the empty cell, the liquid crystal was sealed to produce a liquid crystal display device. Instead of the ITO film,

—The conventional technology was used except that a monomolecular film was formed on the surface of the filter via a silica film.

An image display comparable to that of a conventional liquid crystal display device using an ITO film as a transparent electrode could be performed using the liquid crystal display device formed as described above. .

(Example 14)

In Examples 1 to 13, whether or not the conductive molecules are oriented is determined by forming a liquid crystal cell 170 as shown in FIG. 16 and sandwiching the liquid crystal between polarizing plates 177 and 178, and irradiating light from the back surface. And can be confirmed by observing from the 180 position. The liquid crystal cell 170 has an adhesive 175 with the conductive molecular films of the glass plates 171 and 173, on which the conductive molecular films 172 and 174 are formed, respectively, with the gap between the gaps being 5 to 6 m and the adhesive 175. Then, a liquid crystal composition 176 (nematic liquid crystal, for example, "LC, MT-5087 LA" manufactured by Chisso Corporation) was injected into the inside, and the liquid crystal composition was formed. (1) When the polarizers 177 and 178 are crossed, the orientation directions of the conductive molecular films 172 and 174 are aligned, and this direction is parallel to one polarizer and the other polarizer is Exchange. If the liquid crystal is completely aligned, the liquid crystal will be aligned and become uniform black. If it does not become uniform black, the orientation is poor.

(2) When the polarizers 177 and 178 are parallel, the orientation directions of the conductive molecular films 172 and 174 are aligned, and this direction and both polarizers are parallel. If the liquid crystal is completely aligned, the liquid crystal will be aligned and become uniform white. If the white color is not uniform, the orientation is poor.

If the back substrate is not transparent, use only one polarizing plate on the upper side, irradiate light from the surface, and observe with reflected light.

By this method, it was confirmed that the conductive molecular films obtained in Examples 1 to 13 were oriented.

Industrial applicability

As described above, the present invention can provide an organic thin film having a conductive region that can be used as a conductive wire, a wiring, an electrode, or a transparent electrode. In addition, a high-performance device such as a semiconductor device, a capacitor, a liquid crystal display device, an electroluminescent device, or a solar cell using the organic thin film having the conductive region as a conductive wire, a wiring, an electrode, or a transparent electrode can be provided. Further, electric cables such as coaxial cables and flat cables using the organic thin film having the conductive region can be provided.

Claims

The scope of the claims

1. a terminal binding group covalently bonded to the surface of a base material or the surface of an underlayer formed on the base material; a conjugated bonding group; and an organic molecule containing an alkyl group between the terminal bonding group and the conjugated bonding group. A conductive organic thin film comprising:

The conductive organic thin film, wherein the organic molecules are oriented, and the conjugated group is polymerized with a conjugated group of another molecule to form a conductive network.

2. The conductive organic thin film according to claim 1, wherein the polymerization is at least one selected from electrolytic oxidation polymerization, catalytic polymerization, and energy beam irradiation polymerization.

3. The conductive organic material according to claim 2, wherein the polymerization in the final step is electrolytic oxidation polymerization.

4. The conductive organic thin film _{c according} to claim 1, wherein the conductivity (p) of the conductive organic thin film is 1 S / cm or more at room temperature (without a dopant at 250).

5. The conductive organic thin film according to claim 4, wherein the conductivity (p) of the conductive organic thin film at room temperature (25 ° C.) is 1 × 10 ³ S / cm or more without dopant.

6. The conductive organic thin film according to claim 1, wherein the polymerized conjugated bonding group is at least one conjugated bonding group selected from polypyrrole, polychenylene, polyacetylene, polydiacetylene, and polyacene.

7. The terminal binding group is at least one bond selected from siloxane (one Si〇-one) and Si N— bond (provided that Si and N have another binding group corresponding to a valence). 2. The conductive material according to claim 1, wherein

8. The orientation of the molecules is determined by rubbing orientation treatment, liquid removal from the reaction solution after the molecules are covalently bonded to the substrate surface by a desorption reaction, and polarized light irradiation. 2. The conductive organic thin film according to claim 1, wherein the conductive organic thin film is formed by at least one selected from the group consisting of irradiation treatment and orientation caused by molecular fluctuation during polymerization.

9. The conductive organic thin film according to claim 1, wherein the conductive region of the organic thin film is transparent to light having a wavelength in a visible region.

10. The conductive organic thin film according to claim 1, wherein the molecular unit forming the conductive network is represented by the following chemical formula (A) or (B).

(However, in the chemical formulas (A) and (B), X is hydrogen, an organic group containing an ester group or an unsaturated group, q is an integer of 0 to 10, E is hydrogen or an alkyl group having 13 carbon atoms) , N is an integer of 2 or more and 25 or less, and p is an integer and is 1, 2 or 3.)

11. The conductive organic thin film according to claim 1, further comprising a protective film on a surface of a conductive region of the conductive organic thin film.

12. The conductive organic thin film according to claim 1, wherein the conductive organic thin film further contains a dopant substance.

13. The conductive organic thin film according to claim 1, wherein the conductive organic thin film is a monomolecular film or a monomolecular cumulative film.

14. A terminal functional group that can be covalently bonded to the surface of the base material or the surface of the underlayer formed on the substrate, a functional group that can be conjugated, and a space between the terminal functional group and the functional group that can be conjugated. A chemisorbed compound containing an alkyl group

A substrate surface having active hydrogen or having active hydrogen added to the surface or An organic thin film is formed by bringing it into contact with the surface of an underlayer formed on a base material and covalently bonding by an elimination reaction.

The organic molecules constituting the organic thin film are oriented in a predetermined direction, or are polymerized while being oriented in a polymerization step,

In the polymerization step, a conductive network is formed by forming a conductive network by conjugate-bonding the conjugate-bondable groups to each other by at least one polymerization method selected from electrolytic oxidation polymerization, catalytic polymerization, and energy beam irradiation polymerization. Manufacturing method of thin film.

15. The terminal functional group is an octogenated silyl group, an alkoxysilyl group or an isocyanate group, and at least one dehydrogenation reaction selected from active hydrogen on the surface of the base material, a dehydrochlorination reaction, a dealcoholation reaction, and a desocyanate reaction. 15. The method for producing a conductive organic thin film according to claim 14, wherein a covalent bond is formed by a detachment reaction.

16. The conductive organic material according to claim 14, wherein the conjugate-bondable group is at least one group selected from a pyrrolyl group, a phenyl group, an ethynyl group including an acetylene group, and a ethynyl group including a diacetylene group. Manufacturing method of thin film.

17. The method for producing a conductive organic thin film according to claim 16, wherein, in the final stage of the polymerization step, the conductive network is completed by electrolytic oxidation polymerization.

18 8. The orientation of the molecules is determined by rubbing, decoupling from the reaction solution after covalently bonding the molecules to the substrate surface by a desorption reaction, irradiating with polarized light, and 15. The method for producing a conductive organic thin film according to claim 14, wherein the method is performed by at least one treatment selected from the orientation due to fluctuation.

19. The method for producing a conductive organic thin film according to claim 14, wherein the organic molecule is represented by the following chemical formula (C) or (D).

(However, in the above formulas (C) and (D), X is hydrogen, an organic group containing an ester group or an unsaturated group, Q is an integer of 0 to 10, D is a halogen atom, an isocyanate group or a carbon number. 13 alkoxyl groups, E is hydrogen or an alkyl group having 13 carbon atoms, n is an integer of 2 or more and 25 or less, and p is an integer and is 1, 2 or 3.)

20. The method for producing a conductive organic thin film according to claim 14, wherein the organic molecules are formed in a monomolecular layer.

21. The method for manufacturing a conductive organic thin film according to claim 20, wherein the monomolecular layer forming step is repeated a plurality of times to form a monomolecular layer by stacking monomolecular layers.

22. After repeatedly performing the monolayer forming step and the tilting step alternately, in the conductive network forming step, collectively forming a conductive network in each monolayer of the monomolecular accumulation film, The method for producing a conductive organic thin film according to claim 20, wherein a conductive monomolecular accumulation film is formed.

23. The method for producing a conductive organic thin film according to claim 14, wherein the conductive monomolecular accumulation film is formed by repeatedly performing the monolayer forming step, the tilting step, and the conductive network forming step. .

24. The method for producing a conductive organic thin film according to claim 14, wherein the energy beam is at least one selected from ultraviolet rays, far ultraviolet rays, X-rays, and electron beams.

25. The method according to claim 24, wherein the energy beam is at least one selected from a polarized ultraviolet ray, a polarized far ultraviolet ray, and a polarized X-ray, and the tilt alignment treatment and the formation of the conductive network are performed simultaneously. The method for producing a conductive organic thin film according to the above.

26. The method for producing a conductive organic thin film according to claim 14, wherein a dopant is further added during or after the formation of the conductive network.

27. An electrode made of a conductive organic thin film that is transparent at light wavelengths in the visible light range,

The conductive organic thin film includes a terminal bonding group covalently bonded to a substrate surface or a base layer surface formed on the substrate, a conjugate bonding group, and an alkyl group between the terminal bonding group and the common bonding group. Composed of organic molecules including

The organic molecule is oriented, and the conjugated group is polymerized with a conjugated group of another molecule to form a conductive network.

28. An electric cable comprising a core wire and a conductive organic thin film formed in a length direction of a surface of the core wire,

The electric cable, wherein the organic molecule is oriented, and the conjugated group is polymerized with a conjugated group of another molecule to form a conductive network.

29. The electric cable according to claim 28, wherein the electric cable forms a collective electric wire including a plurality of core wires electrically insulated from each other.

30. The electric cable according to claim 28, wherein the core wire is glass or metal.